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DSHW-2005-001706 - 0901a0688013a463
r> PILOT TEST WORK PLAN FOR PERCHLORATE REMEDIATION PROMONTORY FACILITY PROMONTORY, UTAH Prepared for: June 22,2005 AT1C'51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page i of V June 22, 2005 KLEINFELDER Prepared For: Alliant Techsystems P.O. Box 707 Brigham City, UT 84302-0707 File No.: 51278.001 PILOT TEST WORK PLAN FOR PERCHLORATE REMEDIATION PROMONTORY FACILITY PROMONTORY, UTAH Prepared By: David Jenkins, P.E. Senior Environmental Engineer ^-grk^-^^v^J Project Manager Reviewed By: David L.C6hank, Jr., P.G. ' 0 Project Quality Control Manager Prepared By: KLEINFELDER, INC. 849 West Levoy Drive, Suite 200 SaU Lake City, UT 84123 (801)261-3336 June 22, 2005 ATK/51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page ii of v June 22, 2005 KLEINFELDER TABLE OF CONTENTS SECTION PAGE 1. INTRODUCTION 1 1.1 Pilot Test Objective 1 1.2 Purpose 1 1.3 Scope 1 1.4 Project Staffing and Point of Contact 2 1.4.1 Project StafT 2 1.4.2 Regulatory Point of Contact 2 1.5 Work Plan Organization 3 2. PROJECT BACKGROUND AND SITE CONDITIONS 4 2.1 Overview of Perchlorate Remediation 4 2.1.1 In Situ versus Ex Situ Treatment 4 2.1.2 In Situ Methods 5 2.1.3 Electron Donor Amendment 5 2.2 Results of Bench-Scale Studies 6 2.2.1 Envirogen Study 6 2.2.2 GeoSyntec/SiREM Study 6 2.3 ATK Promontory Facility Site Conditions 7 2.3.1 Geology 7 2.3.2 Hydrogeology 7 3. ADMINISTRATIVE REQUIREMENTS 9 3.1 Pre-Field Activity Plans 9 3.1.1 Schedule 9 3.1.2 Permitting 9 3.1.3 Abbreviated Safety and Health Plan 10 3.1.4 Site Training 11 3.1.5 Field Records 11 3.1.6 Abbreviated Sampling and Analysis Plan 12 3.2 Pilot Test Completion Report 12 4. TECHNICAL REQUIREMENTS 14 4.1 Overview 14 4.2 Mobilization Activities 14 4.3 Groundwater Monitoring 15 4.4 Sparge Well Installation 15 4.4.1 Location 15 4.4.2 Drilling and Soil Logging 16 4.4.3 Construction Requirements 16 4.5 Pilot Test Vapor Sparging 18 4.5.1 System Configuration 18 4.5.2 Groundwater Monitoring Program 20 4.6 Pilot Test Completion Report 21 ATK/51278.00I/SLC5R031 Pageiiiofv June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER TABLE OF CONTENTS (continued) SECTION 5. REFERENCES. PAGE 22 TABLE FIGURES Durations for System Operation 1 Site and Hospital Location Map 2 Pilot Test Vicinity Map 3 Extended Geologic Cross Section 4 Pilot Test Project Schedule 5 Pilot Test Equipment Configuration Schematic APPENDICES A Reference Paper: /« 5/7M Bioremediation of Perchlorate B Abbreviated Safety and Health Plan C Abbreviated Sampling and Analysis Plan ATK/51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page iv of v June 22, 2005 KLEINFELDER ACRONYMS M-g/L micrograms per liter ATK Alliant Techsystems Thiokol Propulsion ASAP Abbreviated Sampling and Analysis Plan ASHP Abbreviated Safety and Health Plan bgs below ground surface CIH certified industrial hygienist DO dissolved oxygen DSHW Division ofSolid and Hazardous Waste fl/day feet per day ft/ft feet per foot mg/L milligram per liter MSDS material safety data sheet ORP oxidation-reduction potential PID photoionization detector psi pounds per square inch PTCR Pilot Test Completion Report Q/D quantity/distance scfm standard cubic feet per minute TDS total dissolved solids UIC Underground Injection Control VOA volatile organic analysis VOC volatile organic compound ATK/Sl 278.001/SLC5R031 Pagevofv June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER INTRODUCTION 1.1 PILOT TEST OBJECTIVE The objective of this pilot test application is to investigate a method for in situ remediation of perchlorate-impacted groundwater. This method involves applying a vapor amendment of mixed ethyl acetate and nitrogen into the subsurface via sparging. The pilot test application will be performed at the Alliant Techsystems Thiokol Propulsion (ATK) - Promontory Facility (the Site), located in Promontory, Utah, as shown on Figure 1. If successful, this application could be applied to remediate perchlorate-impacted groundwater at this Site and the Bacchus Facility. This approach to groundwater remediation requires significantly less cost and maintenance than traditional pump-and-treat methods. 1.2 PURPOSE The purpose ofthe pilot test is to assess if direct injection (sparging) with a vapor amendment of ethyl acetate and nitrogen is efFective at degrading perchlorate-impacted groundwater at the Site. Sparging, as a means of introducing a vapor amendment in situ, is a familiar technology shown to be an effective method of dispersing amendments into the subsurface. 1.3 SCOPE The scope of the pilot test involves drilling a sparge well upgradient of groundwater monitoring well B-6 to approximately 130 feet below ground surface (bgs) as shown on Figure 2. A difhiser will be installed in the well to deliver a gaseous (vapor) form of ethyl acetate and nitrogen amendment for a period of approximately 30 days. Amendment injection rates are estimated to be 5 standard cubic feet per minute (scfm). The vapor amendment will be supplied by a simple system where nitrogen is diffused into liquid ethyl acetate and the resulting vapor is injected into the subsurface via the pressure from the nitrogen supply tank (see Section 4.4.3 for details). A nutrient amendment may also be applied to enhance degradation rates. Groundwater samples ATK/51278.001/SLC5R031 Page 1 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER will be taken before, during, and after the pilot test to evaluate the effectiveness of this technology for degrading perchlorate and to monitor changes in groundwater chemistry at well B-6. 1.4 PROJECT STAFFING AND POINT OF CONTACT 1.4.1 Project Staff Technical design personnel for the work plan include: David Shank Kleinfelder, Project Quality Control Manager (801) 261 -3336 David Jenkins Kleinfelder, Technical Design (916)366-1701 Jen Cowan Kleinfelder, Project Manager (801)261-3336 Technical reviewers and on-site persoimel from ATK include: Chris Busch Project Manager (801) 251 -3562 Paul Hancock Environmental Director (435) 863-3346 Jonathan Hermance Geologist (Bacchus) (801)251-5669 John Holladay Geologist (Promontory) (435) 863-6895 ATK will provide groundwater sampling and analytical services, as they are located near the site and are familiar with groundwater monitoring protocols. 1.4.2 Regulatory Point of Contact The primary regulatory contact for this project is: Mr. Jeff Vandel State of Utah Department of Environmental Quality Division ofSolid and Hazardous Waste (DSHW) P.O. Box 144880 Sah Lake City, UT 84114-4880 (801)538-6170 ATK/51278.001/SLC5R031 Page 2 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 1.5 WORK PLAN ORGANIZATION This work plan is organized to provide guidance on completing a pilot test for perchlorate remediation at the ATK - Promontory Facility. The sections ofthe work plan are as follows: • Section 1 provides the introduction to the project; • Section 2 describes the technology and site background; • Section 3 discusses administrative requirements; • Section 4 lists the technical requirements; • Section 5 provides references related to the project; • Appendix A provides a case study for bench top-scale studies involving perchlorate degradation; • Appendix B outlines safety and health considerations for the pilot test; and • Appendix C details the groundwater sample collection procedures. ATK751278.001/SLC5R031 Page 3 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER PROJECT BACKGROUND AND SITE CONDITIONS 2.1 OVERVIEW OF PERCHLORATE REMEDIATION An increasing number of studies and field tests indicate that perchlorate can be remediated by in situ biodegradation with the addition of an electron donor directly into the subsurface. The objective of in situ remediation is to amend subsurface conditions to stimulate the biodegradation of perchlorate by bringing it into contact with an electron donor such as hydrogen, ethyl acetate, or ethanol. The perchlorate-reducing bacteria then use the combination of oxidant, electron donor, and carbon (either from the donor or, in the case of hydrogen addition, the soil) to chemically transform the perchlorate into organic matter (biomass), carbon dioxide, water, and harmless chloride ions (Cl). The reaction products are shown below: Perchlorate (CIO;) Chlorate (CIO;) Chlorite (CIO;) Chloride (Ct) 2.1.1 In Situ versus Ex Situ Treatment Groundwater remediation in situ offers advantages over ex situ, which requires extracting groundwater. The primary disadvantage of treating extracted groundwater with ex situ remediation through biodegradation is that, in addition to the high initial capitol investment, it requires continuous maintenance of equipment and costly separation and disposal of excess biomass. In contrast, in situ remediation of perchlorate is gaining popularity because, unlike ex situ approaches, it facilitates indigenous microbes in their natural habitat. Thus, there is no waste product requiring costly disposal. Additionally, the costs of amendments for biodegradation are also much less expensive than the costs of resins in an ex situ extract-amend-reinject (or more commonly known as pump-and-treat) system. ATK/51278.001/SLC5R031 Page 4 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 2.1.2 In Sihi Methods Currently, there are several viable engineering methods to introduce amendments (or electron donors) in situ within the saturated zone that are either being proposed, tested, or implemented at perchlorate-impacted sites. These include permeable barriers, direct injection, and vertical treatment wells. Permeable barriers have historically been installed via trenching and slurry injection methods. Amendment injection methods £U"e in the conceptual stages and can involve direct liquid injection, direct vapor injection (sparging), or extract-amend-reinject methods. Vertical treatment wells require active pumping, liquid amendment addition, and reinjection. As described previously, the approach for in situ treatment that was selected for this pilot test is sparging. The benefits of sparging derive from the properties of the vapor. Sparging will minimize the potential for biofouling and maximize the amendment distribution via the diffiasiveness and buoyancy force of the vapor, which will drive the amendment upward through the aquifer. 2.1.3 Electron Donor Amendment Following an evaluation of numerous potential electron donor amendments, Kleinfelder believes that sparging with ethyl acetate has merit for testing and potential full-scale implementation at the Site. Appendix A presents a technical paper that demonstrates acetate as a successful electron donor in bench-scale tests (Envirogen, 2000). Ethyl acetate was selected over acetate because the ethyl group on this molecule will provide additional electron donor capacity. It is our opinion that direct injection of ethyl acetate as an electron donor by sparging is particularly compatible with the site and has the potential to be a cost effective, low maintenance, and successful strategy to significantly reduce both perchlorate and nitrate concentrations in the subsurface. Sodium trimetaphosphate (TMP) may also be added as a nutrient amendment to increase degradation rates. ATKy51278.001/SLC5R031 Page 5 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 2.2 RESULTS OF BENCH-SCALE STUDIES 2.2.1 Envirogen Study As presented in Appendix A, some key observations of perchlorate degradation were made in bench top-scale studies conducted with soil and groundwater from various sites (Envirogen, 2000). Significant observations that were noted include: • Dissolved oxygen (DO), nitrate, and nitrite are degraded preferentially to perchlorate. • Depending on the site, indigenous bacteria may be present in the aquifer. The bacteria can be stimulated to degrade perchlorate with the addition of electron donors. • Sites with low pH values (<6 units) are inhibitory to biological perchlorate reduction. The rate of perchlorate reduction decreased moderately with increases in concentration of salinity (25-50% that of seawater). • Diammonium phosphate was added to provide nutrients (nitrogen and phosphorus) for bacteria growth. 2.2.2 GeoSyntec/SiREM Shidy A laboratory microcosm study performed by SiREM Laboratories demonstrated that indigenous bacteria in ATK's Bacchus Facility aquifer degraded perchlorate with the addition of a soluble electron donor. For the proposed pilot test site at Promontory, we have assumed that similar conditions exist in the aquifer there. According to GeoSyntec, potential groundwater quality impacts of electron donor additions appeared to be limited to mobilization of low levels of dissolved iron and manganese. However, based on other field demonstrations as observed by SiREM, those compounds were expected to ATK/51278.001/SLC5R031 Page 6 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER attenuate to background levels with relatively short distances downgradient fi-om the treatment area (GeoSyntec/SiREM, 2003). 2.3 ATK PROMONTORY FACILITY SITE CONDITIONS 2.3.1 Geology The proposed study area at ATK's Promontory Facility lies to the north of the Great Salt Lake. Here, interbedded sediments from ancient Lake Bormeville overlie alluvial fan deposits and Tertiary lucustrine sediments from pre-Bonneville lakes. Bedrock depths are typically several hundred feet below the ground surface. The generalized cross section that is presented on Figure 3 illustrates the regional hydrogeologic units in this area and is oriented along the approximate longitudinal axis ofthe perchlorate-impacted groundwater plume. The aquifer beneath the study area is a productive zone alluvial sediments consisting of interbedded clays, silts, and gravels that lie above sandstone and semi-consolidated bedrock (see Figure 3). Deeper groundwater wells in the area that penetrate the bedrock do not produce much water from the predominately sandstone and limestone bedrock layers that underlie the study area. 2.3.2 Hydrogeology Recharge to the groundwater table originates as precipitation and run-off along the mountain front. Natural groundwater flow beneath the proposed study area is estimated to be 1 foot per day (ft/day) with a southem gradient direction towards the Great Salt Lake. This was calculated from a hydraulic conductivity of 470 ft/day as obtained from a pump test evaluation of the groundwater conducted by EarthFax (1991), a horizontal groundwater gradient of 0.00067 feet per foot (ft/ft), and a f>orosity of 30 percent. Depth to groundwater was measured at well B-6 at 100.01 feet bgs during groundwater sampling on April 7, 2005. ATK/51278.001/SLC5R031 Page 7 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 2.3.3 Groundwater Chemistry Perchlorate concenfration in samples from well B-6, which is in the area ofthe pilot test location, was approximately 42,000 micrograms per liter (|ig/L) during a sampling event on April 7, 2005. Samples were collected using a downhole pump. Concentrafions of perchlorate appear to have slowly increased in well B-6 since 1991. Total dissolved solids (TDS) and major anions also have high concentrations in groundwater samples from this well. Laboratory results from this event are included in the Abbreviated Sampling and Analysis Plan (ASAP) for this project (see Section 3.1.6). ATK/51278.001/SLC5R03I Page 8 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER ADMINISTRATIVE REQUIREMENTS The following sections describe the pre- and post-construction plans, reports, and adminisfrative requirements to be followed while performing the pilot test near well B-6. 3.1 PRE-FIELD ACTIVITY PLANS 3.1.1 Schedule Figure 4 illustrates the estimated pilot test schedule, with appropriate major and minor project task links. Once this work plan is completed and the sparge well constructed, the injection period will follow for approximately 30 days. If the observed rate of perchlorate degradation is less than desirable after 30 days (i.e., less than approximately 20% reduction of baseline concentration), it will be suggested that sparging continue for an additional 30 days with system adjustments and continued groundwater monitoring. Pilot test results will be complied in a completion report that will be prepared approximately a month after laboratory results are received from post-injection groundwater samples. 3.1.2 Permitting Well Drillins Permit The State of Utah requires a non-production well construction permit for wells deeper than 30 feet. Properly executed permits for the sparge well will be obtained from the Division of Water Rights prior to commencement of well drilling. The driller shall also be licensed as a Water Well Driller in the State of Utah. ATKy51278.001/SLC5R031 Page 9 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER Injection Permit Additionally, the Division of Water Quality also requires that an inventory information form be filled out for the Underground Injection Confrol (UIC) Program. In discussions with the Division, the pilot test will likely be permitted by rule, similarly to the GeoSyntec pilot test at the Bacchus Facility. Hot Work Permit At any time, if work requires the use of a cutting torch or welding device, a Hot Work Permit will be obtained from ATK. This permit requires specific safety protocols to be followed for prevention of accidental fire, explosion, or electrocution. If needed. Hot Work Permits can be obtained through John Holladay, (435) 863-6895 at the Promontory Facility. 3.1.3 Abbreviated Safety and Health Plan An Abbreviated Safety and Health Plan (ASHP) is included in Appendix B of this work plan. The ASHP has been reviewed and approved by Kleinfelder's Certified Industrial Hygienist (CIH) for activities relating directly to Kleinfelder's responsibilities. Field personnel shall be familiar with the requirements of the ASHP and the attached MSDSs for chemicals used as part of the pilot test. A signature page is provided for those required to review the ASHP before commencing fieldwork. Personnel will also be familiarized with special provisions regarding rules and procedures specific to the Site as provided by ATK's facility training. ATK maintains an intemal site-specific health and safety plan for their personnel. However, it is recommended that ATK and other subcontractor personnel follow at a minimum the requirements of Kleinfelder's ASHP for performing sampling activities. ATK/51278.001/SLC5R031 Page 10 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 3.1.4 Site Training Promontory facility-specific training and orientation will be completed before fieldwork begins. This will include viewing a video that addresses site-specific health and safety protocols and procedures needed to obtain security badges and authorization to work on site. This training and orientation program is provided by ATK. John Holladay will be Kleinfelder's site contact at (435) 863-6895 for scheduling the training. Addifionally, contractors will obtain a worksite permit that is contractor and work specific before initiating field activities. 3.1.5 Field Records Field records will be maintained in logbooks. Field logbooks shall be kept and will contain, at a minimum, the information described below. The page numbers, project name, project number, site location, sampling event, project manager, telephone number, and address of contractor office will be listed in indelible ink. The field logbook will be dedicated to the project and maintained by field personnel, who will sign and date it prior to inifiation of field activities that day. The logbooks shall provide a daily record of times, weather conditions, personnel present and their activities, descriptions of fieldwork (drilling, system set-up, sampling, etc.), and unexpected conditions. Entries shall provide factual, detailed, objective information. If authorized by ATK, digital site photographs shall be described and documented in a photo-log sheet with all entries made in ink, signed, and dated. Entries for digital site photographs shall include the project name and number, date of the photograph, weather conditions, the photographer, subject, photo number, and a brief description of the purpose of the photograph. Photographs shall be taken only when accompanied with an ATK employee who has acquired an approved permit for photography. Digital camera memory media shall be emptied before and after use at the site. ATK/51278.001/SLC5R031 Page 11 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER All project field activities shall be recorded on a daily field report form. The daily report shall contain a chronological summary of daily work completed, materials used (including ethyl acetate levels when appropriate), system measurements, weather conditions, safety levels, equipment, and all events pertinent to the work performed in the field that day. Any deviafions from project plans shall also be recorded. Daily field ref>orts will become part ofthe permanent project records and will be included in the Pilot Test Completion Report (PTCR) when the pilot test is completed. 3.1.6 Abbreviated Sampling and Analysis Plan Due to the nature of the pilot test, it is critical to acquire as much information at possible to characterize subsurface conditions during the injection period. Kleinfelder has provided sampling guidance and protocols in the ASAP (Appendix C). It is critical that low-flow sampling techniques be utilized during the pilot test monitoring to minimized disturbance to the anaerobic conditions in the aquifer. 3.2 PILOT TEST COMPLETION REPORT After completion of the pilot test field activities described in Section 4 of this work plan, Kleinfelder will prepare the project PTCR describing the work performed. The PTCR shall be submitted to ATK and DSHW for review and approval. The PTCR shall include: • A summary describing work performed with details ofany deviations from the work plan; • Description of any unexpected conditions encountered during the progress of the work and actions taken to resolve the conditions; • An evaluafion ofthe relative success ofthe pilot test; ATK/51278.001/SLC5R031 Page 12 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER • Conclusions and recommendations regarding the potential for large-scale implementation ofthe ethyl acetate vapor sparge technology at ATK's facilities; • Attachments containing a complete photographic log (as approved by ATK) of the work accomplished; and • Copies of field logbook pages, drilling logs, and analytical results. ATK/51278.001/SLC5R031 Page 13 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER TECHNICAL REQUIREMENTS 4.1 OVERVIEW Given the remote location of the site, ATK will provide groundwater sampling services, and Thiokol Laboratory or Chemtech-Ford Laboratories (depending on the analysis) will provide analytical services. Activities that Kleinfelder and Zimmerman Well Service will be responsible during the pilot test include the following: • Drilling and constructing a sparge well; • Diffiising the vapor amendment (ethyl acetate and nitrogen) into the perchlorate- impacted groundwater; • Nutrient injection (if needed); • Observations ofa subset ofgroundwater sampling events; and • System maintenance and adjustments. 4.2 MOBILIZATION ACTIVITIES The ATK facility engineering department will be contacted for clearing the drilling area of utilities. By law. Blue Stakes will also be contacted at least three days in advance before drilling. It is assumed that ATK personnel on-site will help coordinate with the utility clearance. ATK/51278.001/SLC5R031 Page 14 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 4.3 GROUNDWATER MONITORING Sampling procedures and protocols will follow the ASAP provided in Appendix C. These procedures have been adopted primarily from typical low-flow groundwater monitoring procedures with some modifications specific to the pilot test. Groundwater from well B-6 and possibly T-l will be monitored for a fijll suite of analyses before the pilot test begins and then will be monitored for a subset of analyses during the injection. The frequency will depend largely on the observed rates of degradation and groundwater chemistry response. We have proposed a sampling schedule on Table 1 and Figure 4. During injection, the first three sampling events are offset by three to four days and then the offset is increased for subsequent events. 4.4 SPARGE WELL INSTALLATION 4.4.1 Location ATK's Promontory Facility maintains numerous monitoring wells for the purposes of evaluating groundwater quality in the vicinity of the perchlorate-impacted groundwater. Following discussions with ATK including a review of groundwater conditions and recent perchlorate concentrations, a suitable location for the sparge well has been identified (see Figure 2). The general pilot test location is also indicated on the geologic cross section (see Figure 3). In this area, monitoring well B-6 is near the upgradient end of an area where perchlorate-impacted groundwater contains concentrations exceeding 40,000 [Xg/L. According to the well completion information, well B-6 is completed in the alluvium sediments at a depth of 125 feet bgs. This well location has been selected not only due to the relatively high concentration of perchlorate in groundwater in the area, but also because the underlying aquifer is relatively shallow at this location and access for the pilot test will not interfere with on-going operations at the Site. Additionally, a cross gradient well, T-l, has also been identified for possible monitoring, should groundwater flow have a more westerly direction. Two wells, E-7 and F-5 ATK/51278.001/SLC5R031 Page 15 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. IO KLEINFELDER that are down gradient of well B-6, will not be monitored as they are screened in deeper zones within the underlying bedrock. 4.4.2 Drilling and Soil Logging The sparge well will be installed in a boring drilled by a reverse air rotary drilling rig. Mike Zimmerman Well Service, a State of Utah licensed well driller, was selected to drill the boring and is approved to perform work on ATK property. The boring will be drilled using 6-inch casing; discharged soil cuttings will be observed and logged continuously for lithological informafion. Soil cutting samples will be collected every five feet at a minimum. The boring will be completed to 130 feet bgs, or approximately 30 feet below groundwater. For this pilot test, cuttings from the boring will not require containment and will be spread out onto the surrounding ground surface. 4.4.3 Construction Requirements WeU Details Based on the calculated horizontal groundwater fransport velocity of 1 ft/day (see Section 2.3.2), the sparge well will be constructed approximately 25 feet upgradient of existing monitoring well B-6 at a depth of 130 feet bgs. At this depth, the well bottom will extend approximately 30 feet below the groundwater surface. The sparge well will be constructed with ? inch tubing attached to a specially designed porous tubular ceramic diffuser, which will deliver the vapor amendment into the groundwater. The diffuser will be placed at the bottom of the borehole through the 6-inch drill casing with the tubing extending up to the ground surface. Two in-line check valves will be installed at the surface to prevent groundwater intrusion into the system. A second line, Vi inch in size, will also be installed next to the sparge line down the well. This line may be used for the optional introduction of a nutrient supplement, sodium trimetaphosphate (TMP), for enhancing bacterial ATK/51278.00I/SLC5R03I Page 16 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER degradation of the perchlorate. A check valve will be installed at the end of the line to prevent backflow during injection. The bottom 3 feet of the well around the sparge point and will be filled with #3 Monterey silica sand to allow the vapor amendment to disperse easily into the surrounding aquifer. A 3-foot thick section of bentonite pellets will be used to create a seal above the silica sand. The remainder of the boring will be backfilled with cement-bentonite slurry or other approved armular backfill material to prevent the vapor from migrating to the surface through the boring and provide a surface seal around the well. Details regarding the sparge well design are shown in Figure 5. Svstem Details The sparge line will be equipped with two check-valves at the ground completion end ofthe well. The check-valves will be installed in the vapor amendment supply line above (upstream) the wellhead to avoid backflow and intrusion ofgroundwater into the tubing while the sparge well is depressurized during the pilot test. The nutrient line will also be equipped with a check-valve upstream ofthe wellhead to prevent intrusion ofgroundwater, A pressure release valve will be installed above (upsfream) the check-valves on the sparge line to minimize the potential for the system to become over pressurized (>100 psi). A sample port will be installed above the pressure release valve to monitor the concentration of ethyl acetate and nitrogen vapor exiting the diffiision vessel. Readings will be obtained with a photoionization detector (PID). The target mass load for the vapor is 100 milligrams per liter (mg/L) of ethyl acetate, which was demonstrated to be a desirable amount in the bench-scale study (Envirogen, 2000). The diffusion vessel, which is constructed with type 304 stainless steel, will be fitted with a sight tube to monitor the liquid level of ethyl acetate within the vessel. The diffusion vessel has a capacity of 33 gallons; however, the pilot test will start with 15 gallons of liquid ethyl acetate. The bottom ofthe vessel is also fitted with a drain valve and an 8-inch flange plate for mounting the p>orous nitrogen diffuser. ATK/51278.001/SLC5R031 Page 17 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER Stainless steel tubing will provide the connecfions between the nitrogen supply tank, the diffusion vessel, and the sparge well. A panel containing a regulator flow valve, flow meter, pressure gauge, timer, and solenoid will be connected between the nitrogen supply tank and the diffusion vessel. A solenoid valve and timer will regulate the system operational times. A schematic representafion ofthe diffusion system is included in Figure 5. 4.5 PILOT TEST VAPOR SPARGING 4.5.1 System Configuration The objective of the pilot test system is to diffuse ethyl acetate with nitrogen vapor to act as electron donor when injected into groundwater. The pilot test system will entail the following major components: • Supply tank mounted on a trailer containing 55,000 cubic feet of compressed nitrogen; • Custom-designed stainless steel diffusion vessel for ethyl acetate and nitrogen; • Stainless steel tubing between the tank, panel, vessel, and well; and • The sparge well. Following well completion, the nifrogen supply tank zind diffiision vessel will be connected together with rigid stainless steel tubing. The liquid ethyl acetate will be added to the diffusion vessel from 5-gallon pails using a peristaltic pump or other means to minimize volatilization and potential human exposure (see ASHP). Nitrogen gas, as supplied by the trailer mounted supply tank, will be piped with braided flexible stainless steel tubing to the diffiision vessel where it will bubble through the liquid ethyl acetate under pressure. After the nitrogen gas dissolves the ethyl ATK/51278.001/SLC5R031 Page 18 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER acetate into a vapor, it will then be directed to the diffuser at the bottom of the sparge well. If needed, nutrient amendments wil! be delivered to the bottom of the sparge well by a separate line. The conceptual arrangement ofthe nutrient amendment line is included in Figure 5. Vapor flow through the system will be at a rate of approximately 5 scfin for effective diffasion into the aquifer. Pressure from the supply tank will provide an estimated 30 to 50 pounds per square inch (psi) required to induce flow of the vapor into the sparge well. Some of the advantages ofthis system are that there are no moving parts, the system will make no noise, there is little potential for scaling and biofouling problems, and consumables are exceptionally cost effective. 4.5.2 Applicafion and Operating Schedule Ethvl Acetate The goal will be to maintain a concentration of ethyl acetate at 100 mg/L relative to moving groundwater. Conservatively assuming full equilibrium of ethyl acetate in the diffusion vessel and full dissolution into groundwater, the time to deliver the mass required to reach this concentration in the zone of influence is approximately 1 day. Thus, the system will be operated for 24 hours initially to degrade the perchlorate around the sparge well. Thereafter, the system will be operated intermittenUy for 2 hours every 4 days to maintain degradation of the influx of perchlorate-impacted groundwater. Empirical data gathered from the system start-up will be used to evaluate the assumptions made and to refine the sparging rate and schedule. If the field conditions are similar to the assumptions, then the operating schedule as shown in Table 1 will be used on the pilot test system. However, it is likely that adjustments to the schedule will be made based on actual field conditions. ATKy51278.00]/SLC5R031 Page 19 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER Sodium Trimetaphosphate As indicated in the reference paper provided in Appendix A, a phosphate amendment can be added as a nutrient to enhance perchlorate degradation. An effective phosphate nutrient that has been chosen for this pilot test is sodium TMP. Initially the pilot system will be monitored without any sodium TMP for 2 weeks. If perchlorate is not degraded at desired rate, the nutrient will be added. A concentration of 15 mg/L will be targeted in the aquifer by diluting 10 pounds of sodium TMP powder with water in a 55-gallon drum. Approximately 50 gallons of diluted sodium TMP in water will be injected via a pump through the Vi inch nutrient amendment line that extends to just above the vapor diffiiser. This addition is planned as a one-time application that will have a 24 hour residence time to enable the nutrient to disperse into the vicinity ofthe vapor sparge head. After 24 hours, the sparge system will be activated and the convection ofthe gas diffiision will further disperse the sodium TMP into the aquifer. Following the sodium TMP addition, downgradient well B-6 will be monitored for phosphate and phosphorus during groundwater sampling. 4.5.3 Groundwater Monitoring Program To help maintain a reducing environment, the sparge well and groundwater monitoring wells B-6 and T-l will be capped and sealed from intruding surface air that could potentially affect the anaerobic reactions taking place in the aquifer during the pilot test. If a pump and hose are to be left in the well during the pilot test, a temporary seal will be placed at the wellhead. Details of chemical analyses and sampling methods are provided in the ASAP (see Appendix C). A schedule of proposed sampling dates is shown on Figure 4 and in the ASAP. Pre-injection (Baseline) Conditions Groundwater samples were collected recently to confirm the presence of perchlorate in groundwater beneath the test site. Groundwater samples were collected from well B-6 on April 7, 2005 and results are provided in the ASAP (see Appendix C). Additional pre-injection ATK/51278.001 /SLC5R031 Page 20 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER groundwater samples will be collected before the start-up of the pilot test using low-flow procedures to provide a basis of comparison and establish pre-injection baseline conditions. Monitoring Durine the Injection Period During the pilot test injection period, the groundwater conditions at well B-6 will be monitored for changes in groundwater chemistry and perchlorate concentrations. The injection period is anficipated to extend for approximately 30 days. An expedited 24 hour tum-around-time will be requested from the laboratory for nitrate, perchlorate, and pH/oxidation-reduction potential (ORP) analyses to allow for adjustments to the ethyl acetate concentration or application rates. Also, a downhole-logging probe will monitor the groundwater at well B-6 for pH, conductivity, DO, temperature, and ORP. Samples may also be taken from the cross gradient well T-l for additional information. 4.6 PILOT TEST COMPLETION REPORT Upon completion ofthe field activities described in this work plan, Kleinfelder will prepare the project PTCR describing the work performed as oufiined in Section 3.2. ATK/51278.001/SLC5R031 Page 21 of 22 June 22, 2005 Copyright 2005 Kleinfelder, Inc. Kl KLEINFELDER REFERENCES Envirogen, 2000. In Situ Bioremediation of Perchlorate, SERDP Project CU-1163, Annual Report, December 2000. GeoSyntec/SiREM, 2003. Laboratory Treatability Study to Evaluate Bioremediation of Perchlorate and Chlorinated Solvents in Groundwater (Appendix A of Work Plan), Bacchus Works Facility, West Valley City, Utah, October 2003. ATK/51278.001/SLC5R031 Page 22 of 22 June 22,2005 Copyright 2005 Kleinfelder, Inc. Table 1 Durations for System Operation Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility Pliase Initial Maintenance Day Start 4th day 7th day nth day* Mth day 18th day 21th day 25th day 28th day Date 7/22/2005 7/26/2005 7/29/2005 8/2/2005 8/5/2005 8/9/2005 8/12/2005 8/16/2005 8/19/2005 Approxiiiute Daradon 24 hours 2 hours 2 hours 2 hours 2 hours 2 hours 2 hours 2 hours 2 hours LH 0 4 3 4 3 4 3 4 3 Description System startup and initial vapor delivery Approximately 2 sparge events per week Note: System operation and durations will ultimately be dependent on field conditions. *If deemed necessary, a nutrient amendment of sodium trimetaphosphate will be also added at this time. ATK/51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page 1 of 1 June 22, 2005 Bear River Valley IHC Hospital 440 West 600 North Tremonton, Utah (435)257-7441 —r-r— ) )i'r:^:>Y\ h \. sv '-r'vM^h-k-i^^"K^^^ '.••~v--•~N ^^^ '' . " '^\'^ '-• /'" • •T • : ^ >1 • - -•*^.-~. - '^-——r^. . ^•S''r--.N •y^^1 •• \ -s •• 1 • t'l- ^,. , vl .. •^ •.•••"• ^ '^^ l' -• ~v,i /.•• ••'•' •«». r — — .f^ . 1 !•.••• .'•}••; .«. / ,'; •'.•'•••7 ',^-^--. ••im.. ^i**^' »?- ,'• ""^.ijj^"' '*y..4Yj^ * «... BASE MAP: LAMPO JUNCTION, UTAH U.S.G.S. 7.5 MINUTE QUADRANGLE 1972 2800" 5600' 1" = 4800' CONTOUR INTERVAL 20 FEET * DOTTED LINES REPRESENT 5-FOOT CONTOURS QUADRANGLE LOCATION SLC5Q071.ppt KLEINFELDER Date: 05/03/2005 Project Number 51278.001 Pilot Test Work Plan ATK - Promontory Facility SITE AND HOSPITAL LOCATION MAP FIGURE 1 Note: Perchlorate contours do not incorporate recent well B-6 results. SLC5d149.dwg KLEINFELDER Date: 05/03/2005 Project Number 51278.001 J\. Pilot Test Work Plan ATK - Promontory Facility PILOT TEST VICINITY MAP FIGURE B NORTH Pilot Test Study Area B' NORTH MEAN FEET ABOVE SEE LEVEL DISTANCE / FT LEGEND CLAY SILT SAND ^^-^^^ GRAVEL .'••TTI LIMESTONE "•'• vM SANDSTONE - 4I0D :aOO - 4200 * too Source: Chen Northern, Inc. KLEINFELDER Date: 05/03/2005 Project Number 51278.001 Pilot Test Work Plan ATK - Promontory Facility SLC5Q062.ppt EXTENDED GEOLOGIC CROSS SECTION FIGURE Pilot Test Project Schedule Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility ID "'6 7 8 9 10 11 12 13 14 15 16 17 IS 19 20 21 22 23 24 25 26 27 m TasK Name Pilot Tost Draft Work Plan ATK Review Final Work Plan UDEQ Review Drill Sparge Well Pilot Test System Setup System operation and injection Nutrient Amendment Injection (optional) Additional Injection Monitoring (optional) Groundwater Sampling (Full List) Pre-Sy»i«m Adfusmnem (jfnasdsd) PoM-lnjection Groundwater Sampling (Partial List) GW Sampling l GW Sampling 2 GW Sampling 3 GW Sampling 4 GW Sampling 5 (opti GW Sampling 6 (opi) GW Sampling 7 (opI) Pilot Test Completion Report Draft Completion Report ATK Review UDEQ Review Final Completion Report ^ KLEIN Duration 91 days Iday 19 days Iday 3 days 2 days 3 days 31 edays 1 day 30 edays 46 days Iday 1 day 1 day 36 days 1 day 1 day Iday 1 day 1 day 1 day 1 day 32 days 5 days 8 days 14 days 5 days Start Fri 5/20 Fri 5/20 Wed 5/25 Wed 6/22 Fri 6/24 Tue 6/28 Tue 7/19 Fri 7/22 Thu 8/4 Wed 8/24 Fri 7/22 Fri 7/22 Wed 8/24 Fri 9/23 Tue 7/26 Tue 7/26 Mon 8/1 Fri 8/5 Mon 8/15 Mon 8/29 Mon 9/5 Tue 9/13 Tue 11/8 Tue 11/8 Tue 11/15 Fri 11/25 Thu 12/15 FELDER Finisti Predecessors 4/24 Fri 9/23 Fri 5/20 Mon 6/20 2 Wed 6/22 3FF Tue 6/28 3FS+3 days Wed 6/29 Thu 7/21 Mon 8/22 7FS+1 day Thu 8/4 8SS+12 edays Fri 9/23 8FS+2days Fri 9/23 Fri 7/22 8SS-1 day Wed 8/24 10SS-1 day Fri 9/23 lOFS-lday Tue 9/13 8SS Tue 7/26 12FS+3 edays Mon 8/1 16FS+3 edays Fri 8/5 17FS+3 edays Mon 8/15 18FS+7 edays Mon 8/29 13FS+3 edays Mon 9/5 20FS+4 edays Tue 9/13 21FS+7 edays Wed 12/21 Mon 11/14 14FS+45 edays Thu 11/24 24 Wed 12/14 25 Wed 12/21 26 May 5/1 June 5/8 5/15 5/22 5^9.6/5 ^-sno 3rd Quarter 4th Quarter July August September October 6/12 6/196/26 7/3 7/10 7/17 7/24 7/31 8/7 8/14 8/218/2^^^^1^9/25 10/2 10/9 0/1 4^22 '\E El t^ kH 1] 1 ^ in 0 'H ^ 1 1 J • t_ n •lh 1 r B 1 § 1 T h. November (V2 0/3 11/6 1/1 1 ! 1 ^ ^ ^ t:.:il ^Y 1/2 ^ «- L 1st December Jan /2 12/4 2/1 2/1 2/2 • 1/1 ^^^ ^ 12/15 Figure 4 Pressure Relief Valve With J-tube Panel (Pressure Gauge, Regulatory Flow Valve, Solenoid, Timer) Double Check Valves Nitrogen and Ethyl Acetate Vapor r«i Sight Tube for ^ N / Liquid Level Diffusion Vessel • (304 stainless steel ' 33-gallon) Liquid Ethyl Acetate Nitrogen Gas 8" Nitrogen Ditfuser Drain Valve Developed by: Jenkins NOT TO SCALE SLC5Q064.ppt KLEINFELDER Date: 06/01/2005 Project Number 51278.001 Pilot Test Work Plan ATK - Promontory Facility PILOT TEST EQUIPMENT CONFIGURATION SCHEMATIC FIGURE KLEINFELDER APPENDIX A Reference Paper: In Situ Bioremediation of Perchlorate In Situ Bioremediation of Perchlorate SERDP Project CU-1163 Annual Report Envirogen Inc. 4100 Quakerbridge Road Lawrenceville, NJ 08648 December 01, 2000 1. PROJECT BACKGROUND Ammonium perchlorate (NH4CIO4) has been used for decades in the United States as an oxidizer in solid propellants and explosives The discharge of contaminated effluents from the manufacture of this compound and from the replacement of outdated fuels in military missiles and rockets has resulted in substantial perchlorate contamination in groundwater in several states, including CA, UT, and NV (Utbansky, 1998). Because a sensitive detection method for peichlorate was not available until 1997, the total scope of perchlotate contamination in the U. S. is not yet known However, in a recent study of 232 groundwater samples from CA, approximately 30 % were reported to contain perchlotate at levels ranging from 5 ng/L to 3,700 mg/L (Logan and Kim, 1998). Other states where perchlorate has recently t)een detected in groundwater supplies include NY, IN, IA, PA, TX and AK (EPA, 1999). Perchlorate has t)een manufactured, shipped, or used in at least 43 states nationwide, so the extent of pollution may extend far tjeyond cunent reports (EPA, 1999). The public health concern for ammonium perchlorate is based largely upon the effect of the perchlotate anion on thyroid function Perchlorate blocks the production of thyroid hormone by inhibiting the transport of iodide into the thyroid gland (Wolff, 1998). Because of this inhibitoiy action, perchlorate salts have been used therapeutically in large doses to treat hyperthyroid conditions, such as that resulting from Graves' disease In addition to its inhibitory action, perchlorate has also been reported to lead to an increased incidence of benign tumors in the thyroid of rats and mice when fed at high doses (EPA, 1999). However, the potential risks of low levels of perchlorate exposure to humans through drinking water have yet to be evaluated because data are insufficient. Moreover, with the exception of a few reports of effects on n>etamorphosis in species such as the sea lamptey (Manzon and Youson, 1997) and sand dollar (Saito et al., 1998), few data exist conceming potential ecological effects of perchlotate salts. Thus, the environmental and human health effects tesulting from long-term exposuie lo low levels of perchlorate are largely unknown. Aimnonium peichlorate is very soluble in water and diss(x:iates completely to ammonium and perchlorate ions in aqueous solution. The ammonium ion is leadily assimilated by microorganisms as u nutrient, whereas the perchlorate anion (CIO4) is mobile and persistent; theiefore. it is the peichlorate anion that is the main contaminant present in groundwater at nx>st sites. Standard practices are not effective at removing perchlorate from wastewater because the compound is nonreactive and nonvolatile, its salts are highly soluble, and it can not be reduced by common reducing agents (Urbansky, 1998). Water treatment technologies such as sedimentation, air-stripping, ion exchange, carbon adsorption, reverse osmosis, and advanced oxidation have not proven to be viable options for peichlorate removal from water (Logan, 1998; EPA, 1999). Unlike abiotic approaches, however, biological treatment represents a pronnising technology for perchlorate remediation in giound and surface water Several microbial strains have been isolated widi the ability to degiade perchlotate by using the molecule as a terminal electron acceptor (Attaway and Smith, 1993; Rikken et al, 1996; Wallace et al., 1996; Logan, 1998) The enzymatic pathways involved in perchlotate reduction have yet to be fully elucidated. However, van Gtnkel et al. (1998) suggest that a perchlorate reductase enzyme catalyzes an initial two-step reduction of perchloiate (CIO4') to chloiate (CIO3) and then chlorite (ClOV). The chlorite is further reduced by chlorite dismutase to chloride (Cl) and oxygen (O2). Thus, mictobial degiadation of perchlorate yields two innocuous products, chloride, and oxygen. In addition, the reduction of perchlorate to chloride is a very favorable process from a thennodynamic perspective. Thus, bacteria capable of using perchlotate ate likely to have a distinct ecological advantage in contaminated environments The key to utilizing peichloiate-reducing bacteria for in situ remediation is undeistanding the conditions that limit their activity in subsurface enviionments and then devising effective technologies to overcome these limitations and subsequently stimulate perchlorate degradation. Full-scale bioreactor systems have successfully been developed by Envirogen as well as researchers at Tyndall Aii Foice Base for ex situ perchlorate treatment. However, to date, little research has been conducted to develop an in situ technology for perchlorate bioremediation The development of such a technology is the goal of this project IL PROJECT OBJECTIVE The objective of this project is to develop a biological treatment technology for in situ remediation of perchlorate in subsurface environments. The development of an effective technology for in situ perchlorate remediation requires a fundamental undeistanding of the conditions that limit biological perchlorate reduction in groundwater and the most effective means to overconne such limitations. This research effort is designed provide this fundamental understanding. We hypothesize that four key factors may be contributing to the persistence of perchlorate at various subsurface sites. These key factors and our approach to their evaluation in this research effort aie as follows: (1) Absence of an appropilate substrate (electron donor) for growth of indigenous perchlorate-degrading bacteria. Based on preliminary studies, we believe that the absence of an oxidizable substrate is the key factor limiting biological perchlorate degradation at many subsurface sites. Therefore, experiments will be conducted using aquifer samples ftom contaminated field sites to evaluate the potential of numerous organic and inorganic electron donors to stimulate perchlotate reduction in situ. The most promising electron donors will be tested in a flow-through aquifer system to provide relevant kinetic data for modeling and field trials. (2) Presence of alternative electron acceptors for bacterial respiration, including O2, NO3', and NO2 in groundwater. Perchlorate serves as an electron acceptor for bacteria during anaerobic respiration. The mictobial reduction of one electron acceptor is frequently influenced by the presence of others (eg., oxygen inhibits dissimilatoiy nitrate reduction) The geneial relationship between perchlorate and other common electron acceptors is unclear. However, nitiate, nitrite, and oxygen have been observed to inhibit peichloiate reduction by a few bacterial cultures (Attaway and Smith, 1993; Logan, 1998). Because each of these molecules as well as other electron acceptois such as sulfate and iion are frequently present in groundwater, understanding their influence on microbial perchloiate reduction is critical to successful remediation efforts. Experiments conducted during this project are designed to assess the influence of common electron acceptors, such as oxygen and nitrate, on perchloiate degradation by naturally occurring bacteria in field samples and by microbial isolates (3) Lack of an indigenous population of bacteria capable of perchlorate reduction. In some environments, bacteria with the metabolic enzymes to reduce perchloiate to chloride may be absent. In such cases, augmentation with exogenous microorganisms will be requiied for in situ remediation. As part of this research effott, bacterial stiains and consortia will be isolated from Envirogen's FBR systems that are cuirently treating perchlorate and from aquifer samples collected from perchlorate-contaminated sites. The potential for diese stiains to degrade peichlorate in situ under relevant environmental conditions will then be evaluated in microcosm and column studies- (4) Unfavorable environmental conditions for activity of indigenous perchlorate degraders. The role of environmental vatiables on in situ perchlotate degradation has not been extensively studied. In addition to evaluating the effect of electron acceptors such as nitrate on peichlorate reduction, experiments will be undeitaken to look at the effect of salinity (ionic strength), pH, and co-contaminants on microbial peichlorate degiadation These factors may be extremely impoitant at specific sites (eg., salinity in groundwater at coastal sites) but, as yet, they have not been investigated. The research performed during this project is designed to provide extensive information on (1) the potential for successful perchloiate remediation at subsutface sites by addition of electron donors (i.e., biostimulation); (2) the most effective electron donors to use in biostimulation effoits, and the expected concentrations and remediation kinetics achievable with these donors; (3) the possibility for successful bioaugmentation (i e., injection of bacterial isolates) for subsurface perchlorate remediation; and (4) the probable influence of alternate electron acceptors and environmental variables on perchlorate reduction during biostimulation and/or bioaugmentation efforts. These data will provide the fundamental knowledge required for the design and implementation of pilot-scale and full-scale remediation efforts at perchloiate contaminated sites. III. TECHNICAL APPROACH The research tasks to conducted during year 1 ofthis project are detailed in the following section Task 1. Collect Aquifer Solids and Groundwater from Field Sites. Aquifer samples were collected from four jperchlorate-contaminated locations: (1) the Jet Piopulsion Laboratoiy (JPL) in Pasadena, Califomia, the Indian Head Division Naval Surface Warfare Center (MDIV) in Indian Head, Maryland (2 field sites), and a commercial facility in the Rocky Mountains. Aquifer solids and groundwater were obtained from the first three locations, and groundwater only was obtained from the Rocky Mountain site. These samples were used in microcosm studies to represent a range of different environments that have experienced perchlotate contamination. Samples have also been collected from one pristine site in South Oyster, Virginia, but results are not yet available- Task 2. Obtain Microbial Consortia and Individual Bacterial Isolates Capable of Perchlorate Degradation. Envirogen has constructed a full-scale fluidized bed reactor (FBR) biotieatment system for degrading perchlorate in groundwater at the GenCoip Aerojet facility in Rancho Cordova, Califomia The reactor system, which uses granular activated carbon as a matrix and ethanol as an elecuon donor, is currently reducing perchlorate levels in feed water from approximately 4 mg/L to non-detectable levels (< 5 ^g/L) at flow rates of greater than 3,000 gallons per minute Food processing waste was used as the original inoculum for the FBR system. The bacteria responsible for perchlorate degradation in these reactors have not been identified. The objective of this task was to isolate individual perchlorate degrading bacteria or a mixed bacterial culture from the pilot FBR system- In addition, bacterial isolation techniques were used to enrich and isolate cultures from all of the field sites. Task 3. Identify Conditions Required for In Situ Biostimulation of Perchlorate Degradation. The objective of this task was to develop an understanding of the factors promoting perchlorate degradation in subsurface environments as well as the conditions that inhibit the piocess- Small-scale lal>oratory miciocosms were used to evaluate both biostimulation of indigenous perchlorate degrading microbes and the addition of exogenous perchlorate degiaders (isolated during Task 2) for aquifer remediation. The factors that were evaluated in these studies include: (A) choice of electron donor (substrate) for growth of perchloiate-degrading bacteria, (B) the influence of dissolved oxygen, nitrite, and nitrate on perchlorate removal, and (C) the role of environmental factors including salinity (ionic strength), groundwater pH, and presence of organic co-contaminants on peichlorate degradation. Detailed Methods and Results for Each Research Task are provided in the following section. IV. PROJECT ACCOMPLISHMENTS. A. JET PROPULSION LABORATORY (JPL). Groundwater samples and well-bottom sediments were collected from the Jet Propulsion Laboratoiy (JPL) on April 27, 2000. These samples were used in a series of microcosm studies (Task 3) to evaluate (1) the most effective electron donors for the stimulation of perchlorate-ieducing bacteria at the site (adding substiate but not bacteria); (2) the possibility for successful bioaugmentation (i.e., injection of bacterial isolates) for subsurface perchlorate remediation; (3) the influence of altemate election acceptors (nitrate, nitrite, and oxygen) on perchlorate degradation; and (4) the roles of two environmental variables, pH and salinity, on perchlorate degradation. Sanipie CoUection. Groundwater: Groundwater was collected from nranitoring well 7 (MW-7) at the JPL site. Aseptic sampling techniques and sterile sample containers were used to prevent contamination of groundwater with non-native bacteria. Aquifer Solids: Aquifer core samples were not collected for these studies. The extreme depth to contaminated groundwater at JPL (> 200 ft) makes collection of subsurface solids problematic and expensive. However, a bailing device was used to collect sediments from the bottom of MW-7 The well sediments provided sediment material (and associated microflora) for microcosms. Microcosms were set up using groundwater only and gioundwater mixed with solids from the bottom of the well. Microcosm Studies- Electron Donor Addition and Bioaugmentation. Methods: Small-scale laboratory microcosms were used to evaluate both biostimulation of indigenous perchloiate- degrading microorganisms and the addition of exogenous perchlorate degraders for aquifer remediation at JPL (Figure 1). Microorganisms capable of degrading perchloiate utilize the molecule as an electron acceptOT duiing growth on either an organic or inorganic substrate (electron donor). The absence of an appropriate electron donor in subsurface aquifers contaminated with perchlorate is probably one of the key factors leading to its persistence in situ. The factois influencing the choice of substrate to promote perchlorate biodegradation are likely to include the physiology of the perchlorate-degiading strains, the character of the natural microflora competing with those strains for growth, and the geochemistry at the site. The objective of this phase of work was to test a variety of substrates in groundwater samples collected from JPL and determine which substrates, if any, are most efficient at stimulating perchlorate reduction. Microcosms to evaluate perchlorate degiadation were prepared in sterile, i60-ml seium bottles. All experimental work was performed in a Coy Environmental Chamber with a nitrogen headspace. In one study, groundwater and well solids (silty mateiial) were mixed together in a ratio of approximately 6:1 in a large sterile bottle. The slurry material was amended with a sterile stock of diammonium phosphate to provide nitrogen (5 mg/L as NH4) and phosphorus (4.5 mg/L as P) as nutrients for bacterial giowth, then 120-mL volumes were added to semm bottles. Triplicate serum bottles were amended with one of the following substrates to 200 mg/L: methanol, ethanol, acetate, benzoate, lactate, sucrose, molasses or a mixture of ethanol/yeast extract (100 mg/L each). Triplicate bottles also received hydrogen gas or propane in the headspace as gaseous substiates. Seveial microcosms were inoculated with one of two different perchlorate-degiading enrichments that have been isolated at Envirogen. Acetate and ethanol/yeast extract were tested as electron donors in these samples. Triplicate samples were prepared without any substrate, and triplicate bottles received formaldehyde (1 %) to inhibit all biological activity All bottles were crimp-sealed with sterilized Teflon-lined septa and incubated at I5°C to approximate HJ situ temperatures. At 10, 21, and 35 days of incubation, a 20-ml subsample was removed from each bottle- The samples were analyzed for perchlorate by ion chiomatography (IC) using EPA Method 314.0. A second microcosm study was conducted using only groundwater collected fiom MW-7 (i.e , no sediment). Sterile seitun bottles received 120-ml ofgroundwater and acetate, yeast extract, methanol, or molasses at a concentration of 200 mg/L. Microcosms without added substrate were also prepared as were killed controls (1 % formaldehyde). Sampling and analysis were conducted as described foi the previous study. Results: The water collected from well MW-7 contained perchlorate at 307 |ig/L (ppb). The water also contained nitrate at a starting concentration of 18.6 mg/L (as NOj) sulfate at 44 mg/L, 140 mg/L of alkalinity (as CaCOj) and dissolved oxygen at 2.6 mg/L. Sediment/Groundwater Microcosms The starting perchloiate concentiation in microcosms prepared with groundwater and sediments was 310 mg/L. The initial pH was 7.6. The microcosms also contained high levels of ferric iron (> 600 mg/L), which was present in the sediment sample. The iron was probably well casing that had oxidized and settled to the well bottom After 10 days of incubation at IS'C, perchlorate levels weie below detection (MDL; 5 Ug/L) in microcosms amended with acetate, ethanol, ethanol/yeast extract, lactate and molasses (Table 1) The perchlotate concentrations in ail samples augmented with exogenous peichlorate-degrading bacteria (cultures FBR2 or PCl) were also below detection aftei 10 days. After 21 days of incubation, perchloiate was below detection in all live samples except those amended with benzoate as an electron donor. Interestingly, perchlorate was also degraded in samples without added electron donor An organic or inorganic election donor associated with the well sediments (e.g., reduced iron, natural organic matter) probably supported biological perchlorate reduction in these samples This hypothesis is supported by the observation that perchlorate was not degraded in groundwater samples without electron donor added (see next section). No perchloiate loss was evident in samples that were treated with formaldehyde to inhibit biological activity. It should be noted that nitrate was also degraded to below detection in the live aquifer microcosms, but not in killed controls (data not shown). Groundwater Microcosms: Perchlorate degradation was somewhat slower in microcosms containing groundwater compared to those with sediments (Figure 2). However, after 21 days of incubation, perchlorate was below detection (5 ^g/L) in triplicate samples amended with acetate. Appreciable degiadation of perchlorate was also observed in samples amended with yeast extract or molasses. Perchlorate was not degraded in samples treated with methanol as an electron donor or in those without added electron donor. The killed samples (1 % formaldehyde) also showed no loss of perchlorate. Conclusions: The results from the microcosm study using aquifer samples from JPL suggest the following: (1) indigenous bacteria capable of degrading perchlorate are present in the aquifer underlying JPL; (2) diese bacteria can be stimulated to degiade perchlorate by the addition of electron donors; and (3) perchlorate levels can be reduced to lielow 5 ^g/L thiough biostimulation. The fact that perchlorate degradation was observed in gioundwater microcosms, without sediment, is veiy promising, since microbial biomass in aquifers is usually associated primarily wilh solids. Microcosm-Studies - Influence of Alternate Electron Acceptors. Methods: The objective of this study was to deteimine the influence of oxygen, nitrate and nitrite on perchloiate degradation by natural microflora in aquifer samples fiom JPL Aquifer microcosms weie used to assess the role of these molecules on perchlorate reduction by natural microflora in the subsurface samples. Based on results from the previous study of electron donors, ethanol was chosen as the electron donor foi these experiments. The microcosms were set up as described in the previous section (160-ml setum bottles, 120-ml aquifer slurry of sediments and groundwater). Eight microcosms were initially amended with perchlorate to provide a starting concentration of 100 mg/L The remaining samples did not receive additional perchloiate (~ 300 ^g/L starting concentration). Duplicate miciocosms at an initial concentration of 100 mg/L peichlorate received the following treatments (1) ethanol only (100 mg/L); (2) ethanol (100 mg/L) and NOj (IOO mg/L); (3) nitrate only (100 mg/L) (i.e., no ethanol); or (4) edianol (100 mg/L), NO3 (100 mg/L), and foimaldehyde (Killed Conlrol). To evaluate the role of nitiite (NOi) on perchloiate degradation, duplicate bottles were amended widi the following (1) ethanol (100 mg/L) and 1 mg/L nitrite; (2) ethanol (100 mg/L) and iO mg/L nitrite; or (3) ethanol only. A killed control was also prepared for this study by adding 1 % formaldehyde to one set of duplicate samples. In a thiid study, the effect of oxygen on perchlorate degiadation was determined by oxygenating the headspace of two Ixittles containing 300 ng/L perchlorate and ethanol (100 mg/L). The samples were incubated at I5°C- Aqueous subsamples were periodically removed from each microcosm for perchlorate analysis by EPA Method 314 0 and analysis of nitrate and nitrite by EPA 300.0 series methods. Results: There was no loss of perchloiate, nitiate, or nitrite in any of the sampies that were treated with formaldehyde to inhibit microbial activity. Thus, all reductions in the concentrations of these anions in aquifer samples are assumed to be biological. Nitrate was degraded before perchloiate in samples that received both anions at inilial concentrations of 100 mg/L (Figure 3). Nitrate was reduced to below detection after only 4 days of incubation, with no apparent lag period. Nitrite, which is the initial product in biological denitrification and nitrate reduction, was detected in samples at day 4, but this anion was also degraded to below detection by day 7. A lag period of approximately 16 days occurred before perchlorate degradation cwnmenced in these microcosms. However, perchlorate was reduced from 100 mg/L to below detection (< 5 Jig/L) between day 16 and day 28- Interestingly, the degradation of perchlorate was slightly more rapid in samples that were initially amended with nitrate to 100 mg/L compaied to those that did not teceive the anion (Figure 4). This may reflect the growth of a population of denitrifying bacteria (stimulated by nitrate addition) that subsequently degraded perchlorate Samples that were not amended with ethanol as an electron donor showed no perchlorate degradation during a 22-day incubation period (Figuie 5). In these same samples, however, nitrate levels declined from 100 to approximately 40 mg/L during the initial 7 days of incubation. During this same time, levels of nitiite in the samples increased from below detection to nearly 40 mg/L. On a molar basis, this represents a nearly stoichiometric reduction of nitrate to nitrite. Thus, the data show that nitrate was biologically reduced to nitrite, but not further (i.e., to nitrogen gas or ammonia) in the absence of an added electron donor. The substrate supporting this reaction is unclear, but may be organic matter associated with the well-bottom sediments- Like nitrate, nitrite added to aquifer microcosms at either 1 or 10 mg/L was degraded before perchlorate (data not shown). The addition of nitiite at these levels did not appear to influence the rate of perchlorate degiadation (i.e. after the initial lag period, the rate of perchlorate reduction was the same in samples with and without added nitrite). The degradation of perchlorate was completely inhibited by the presence of oxygen in aquifer samples (Figure 6). This result confirms previous findings than peichlorate degiadation occurs only under anoxic conditions. Conclusions: The results from this set of experiments suggest that nitrate and nilrite are degraded preferentially to perchlorate in this subsurface environment. It is unclear from the results whether the presence of nitiate or nitiite actually inhibits biological perchlorate degradation, however, in no instance was peichlorate degiadation observed until t>oth of these competing electron acceptors were degraded in the samples. An undeistanding of the relationship between perchlorate and comjpeting electron acceptors (eg., oxygen, nitrate, nitrite, ferric iron) is important l)ecause these molecules fiequently occur with perchlorate in groundwater For example, the groundwater collected from JPL contained 18.6 mg/L of nitrate but only 300 )ig/L or perchlorate. Therefore, an understanding of whether nitrate impedes perchloiate degradation (i.e., due to enzyme inhibition or other factois) may be important in evaluating tieatment options at contaminated sites. Addittonal experiments are planned with microcosms, flow-through columns, and perchlorate-degrading cultures to better assess the influence of nitrate and other electron acceptors on perchlorate degradation. Microcosm Studies - Influence of Environmental Conditions on Perchlorate Degradation. Methods: Little infoimation exists on the influence of environmental variables such as temperature, pH, salinity, redox potential, alkalinity, and the presence of additional contaminants on biological degiadation of perchlorate in groundwater. The influence of two environmental variables, pH and salinity, on perchl<xate degradation was tested using aquifer samples from JPL. To assess the influence of salinity on perchlorate removal in field samples, a synthetic seawater medium was prepared at 0.5X, IX, and 2X concentrations The stocks were then mixed 1:1 with groundwater from the field site yielding salinities ranging from 0.25 X to I X that of seawater. The samples were then amended with perchlotate back to initial concentration (- 300 ^g/L). Ethanol was used as the electron donor in these studies Killed controls were prepared at each level of salinity by adding formaldehyde to samples to a final concentration of I %. All microcosms were prepared and incubated under anoxic conditions. Aqueous subsamples were removed periodically and analyzed for peichlorate as described previously. The role of pH on perchlorate biodegradation was evaluated essentially as described for salinity. In this case, however, the pH rather than the ionic strength of the aquifer material was manipulated. Because the buffering capacity of groundwater is limited, MES buffer was added to samples at a concenttation of 2 mM to maintain pH at desired levels. The slurry material was then divided into 5 sterile beakers in the anaerobic chamber and the pH of each sample was adjusted using sterilized HCl or NaOH, The final pH levels ofthe slurries were 4.0, 5.0,6.0, 7.0, or 8.0 The pH-adjusted slurry material was then added to sterile 160-ml serum bottles in triplicate. One bottle at each pH was amended with formaldehyde to a ftnal concentration of 1% to inhibit microbial activity. Aqueous subsamples were removed from each sample at vaiious times during incubation at IS'C and analyzed for perchlorate by EPA Method 314.0. Results and Conclusions: Salinity: The rate of perchlorate degradation in microcosms prepared from the JPL aquifer samples declined moderately with increasing salinity (Figure 7). During a 29-day incubation period, the perchloiate concentration in samples containing salinity at 25 or 50 % that of seawater declined from a starting concentration just above 0.3 mg/L to below detection (< 0.004 mg/L). The perchlorate concentration in samples brought to the salinity of seawater (~ 3 % total salinity) also declined during 29 days, but approximately 0 15 mg/L remained at the end of the incubation peiiod. pH: The biodegradation of peichlorate was most rapid in JPL aquifer samples brought to a pH of 8.0 (Figuie 8). Levels of perchlorate declined from approximately 0.25 mg/L to less than 0 004 mg/L in 28 days. Perchlorate was also completely degraded in samples at a pH of 7.0 during the 28-day incubation. However, at pH values of 4.0, 5.0, and 6.0, little or no perchlorate losses were obseived in the aquifer microcosms. These results are supported by data from a second site (THDFV) that suggest that low pH is inhibitoiy to perchloiate reduction in environmental samples (see next section). B, INDIAN HEAD DIVISION, NA VAL SURFACE WARFARE CENTER (IHDIV). Sample Collection. Aquifei solids and gioundwater were collected from two separate locations at IHDfV on August 1, 2000 using a Geoprobe (Figure 9 & 10). The extent of perchlorate contamination in the shallow aquifer at this site is unknown, so sampling locations were chosen based on historical use and disposal of perchlorate at the site. The initial sample site was the drainage aiea behind a propellant mixing facility at fHDIV (Building 1170 site). The level of the water table at this site is approximately 4 ft below grade. Sediments were collected from 4 to 12 ft and gioundwater from 6 to 12 ft below grade. The second sample location was an open meadow behind the rocket "hogout" facility at IHDrV (Hogout site). Solid fuel is removed from rockets and missiles in this building using a high-piessure washout piocedure (i e , "hogout" procedure). Before 1996, the washout water was discharged tiirough the region where the field samples were collected. Sediment samples fiom 2 to 13 ft below giade were collected and homogenized. Groundwater was taken from 6 to 12 feet below grade at the site. Microcosm Studies - IHDIV Building 1170 Site. Methods: General Preparation and Sampling: All experimental work was performed in a Coy Environmental Chamber with a nitrogen headspace. Sampling for analysis of perchlorate and other parameters was performed outside of the chamber. Prior to sample collection, a volume of nitrogen gas was added via syringe to the headspace of each microcosm bottle. The addition of nitrogen created backpressure in the bottle to facilitate sample withdrawal. More impoitantly, this method ensured that no oxygen was introduced into the bottles during sampling. All samples were analyzed for perchlorate by ion chromatography (IC) using EPA Method 314 0. Evaluation of Electron Donors: Microcosms to evaluate the inftuence of different electron donois on perchlorate degradation were prepared in sterile, 160-ml serum bottles. Gioundwater from the Building 1170 site was amended with a sterile stock of diammonium phosphate to provide nitrogen (5 mg/L as NH4) and phosphorus (4.5 mg/L as P) as nutrients for bacterial growth. Groundwater and sediment ftom the site were added to each 160-mL bottle at a ratio of approximately 3:1 (100-mL groundwater and 30-g sediment) Each bottle was spiked with a filter-sterilized sodium perchlorate stock solution to a final perchlorate concentration of 125 mg/L. Triplicate serum bottles were amended with acetate, ethanol, or molasses to 200 mg/L. Triplicate bottles also received hydiogen in the headspace as a gaseous substrate. Triplicate bottles were inoculated with a perchloiate-degrading enrichment (FBR2) isolated at Enviiogen; ethanol was tested as electron donor in these bottles. Killed controls were prepared with acetate as a substrate and I % formaldehyde to inhibit all biological activity. The bottles were crimp-sealed with sterilized Teflon-lined septa and incubated at 15°C to approximate i;i situ temperatures. At 11, 19, and 34 days of incubation, a 15-inl subsample was removed ftom each bottle. Preservation of the samples was accomplished by passing the water through sterile nylon filters and storing at 4°C until analysis Electron Donor Concentration: The objective of this study was to detennine the amount of electron donor needed to support perchlorate reduction, and to compare tbe actual electron donor lequiiement to the theoretical requirement. Acetate was used as an electron donor (based on results fiom the previous study), and the quantity required to degrade a given quantity of perchloiate in aquifei microcosms was determined. Miciocosms wete prepared in sterile, 60-mL semm tmttles. Nuttient-amended groundwater and sediment were combined in each bottle at a ratio of about 4.5:1 (45-mL groundwater and 10-g sediment). Each bottle was spiked with a filter-sterilized sodium perchlorate stock solution to a final perchloiate concentration of 100 mg/L (109 mg/L actual measured). Sodium acetate was added to triplicate bottles at concentrations of 0, 10, 25, 50, 75, and 100 mg/L as acetate. One killed conlrol was prepared by adding 1 % formaldehyde to a miciocosm containing 100 mg/L acetate All bottles were crimp-sealed with steiilized Teflon-lined septa and incubated at 15°C to approximate in situ temperatures At 4,6, 8, 10, and 13 days of incubation, a 7-mL subsample was removed from each bottle. The samples were filtered and exposed to air, then frozen to inhibit any additional perchlorate or acetate degradation Perchlorate concentrations were measured in each sample using EPA Method 314.0. Results: Groundwater Analysis: The groundwater collected ftom the Building 1170 site did not contain perchloiate (< 0.004 mg/L), nitrate (< 0.02 mg/L) or nitiite (< 0.002 mg/L) above detection limits. Sulfate was present at 12 mg/L, chloride at 43 mg/L, and alkalinity was 40 mg/L (as CaCOs). The pH of the water was 5.9. A slurry containing 30 g of sediment and 100 mL of water had a pH of 6 1. Evaluation of Electron Donors: Perchlorate was not detected in samples collected ftom the Building 1170 site, so the aquifer microcosms were amended with the anion to a starting concentration of 125 mg/L. After 11 days of incubation at IS'C, peichlorate levels were below detection in microcosms amended with hydrogen gas (Figure 11). Samples that received acetate declined to 3 mg/L total perchloiate during this time. After 34 days of incubation, perchlorate was below detection in samples treated with molasses or acetate, as well as those receiving hydiogen as an electron donor Samples receiving ethanol as an electron donor showed no appreciable decline in perchlorate levels- Likewise, no perchlorate loss was evident in acetate-amended miciocosms that received formaldehyde to inhibit biological activity. The perchlorate concentration in live samples that did not receive any exogenous substrate declined from 126 to 76 mg/L during 34 days of incubation. A similai decline was previously observed with JPL microcosms containing gioundwater and sediments (but not gioundwater only). This decline suggests that an electron donor present at the site, such as natuial organic matter or an organic co- contaminant, may support degradation of perchlorate at this location. The absence of detectable perchloiate in this region, which seived as a deposition area for washdown water from the 1170 facility, further supports this hypothesis. Electron Donor Concentration: Based on stoichiometric calculations, the quantity of acetate required for a bacterium to degrade perchloiate is 0 61 mg per mg perchlorate. This latio was tested in natural samples from the Building 1170 location by varying the acetate dose added to microcosms and evaluating peichlorate degradation. Miciocosm samples initially received 100 mg/L of perchlorate and either 0, 10, 25, 50, 75, or 100 mg/L of acetate. After 10 days of incubation, samples amended with 100 or 75 mg/L of acetate no longer had perchlorate at detectable levels (Figure 12). After 13 days, concentiations of perchlotate in samples amended with 50 mg/L of acetate were also below detection and samples treated with 0, 10, and 25 mg/L acetate had mean perchlorate levels of 81, 52, and 41 mg/L, respectively. The quantity of acetate required for complete removal of perchlorate from the miciocosm samples was less than determined from reaction stoichiometry. However, as observed in (Mrevious samples ftom this site, peichlorate degradation occiured in unamended samples, presumably supported by natural organic materials at the site. When this loss is taken into account, the perchloiate degradation obseived with different levels of acetate become much closer to that expected based on theoretical calculations These ratios ore presented for 10,25, and 50 mg/L acetate in Figure 12. Additional studies conceming the ratio of election donor required for perchlorate degradation in natural samples wil] be conducted in flow- through column studies in Year 2. Conclusions: The results from the microcosm study using aquifer samples from the Building 1170 site suggest the following: (1) indigenous bacteria capable of degrading perchlorate aie present in the shallow aquifer in the vicinity of Building 1170, and (2) these bacteria can be rapidly stimulated to degiade perchlorate to below 0.004 mg/L. by the addition of several election donors- The data also suggest that natural attenuation of perchlorate is possible at this location. This area was used for the disposal of perchlorate- containing wastewater from the mixing facility until 1998, yet the anion was not detected in subsurface samples, which suggests attenuation by eithei transport or biodegradation. In addition, samples amended with perchlorate but no electron donor showed significant losses of the anion in microcosm studies. A natural electron donor (eg., humic material) or an organic co-contaminant most likely served as an electron donor for biological perchlorate reduction in these samples. Microcosm Studies - IHDIV Hogout Facilitv. Methods: Electron Donor Addition: A second microcosm study was conducted using gioundwater and sediment collected from the Hogout site at IHDIV. The experiment was prepared in the same manner as described for the previous study, except that no perchlorate addition was lequired. The starting perchlotate concentration in the mixed groundwater and sediment was approximately 45 mg/L. Triplicate semm bottles were amended with nutrients (N and P from diammonium phosphate) and one of the following substrates at 2(K) mg/L: methanol, ethanol, acetate, benzoate, lactate, sucrose, molasses, or a mixture of ethanol and yeast extiact (100 mg/L each). Triplicate bottles also received hydrogen gas or propane in the headspace as gaseous substrates- Triplicate bottles were inoculated with the perchlorate-degiading enrichment FBR2; ethanol was used as an electron donor in these bottles. In addition, triplicate miciocosms were prepared with nutrients (N and P) but no substrate, substrate (acetate) but no nutrients, and without addition of substrate or nutrients Killed control samples were prepared with acetate and received formaldehyde (1 %) to inhibit all biological activity. All bottles were crimp-sealed with stetilized Teflon-lined septa and incubated at 15°C to approximate in situ temperatures. At 11, 20, 36, and 71 days of incubation, a 15-mL subsample was removed from each bottle. The samples were preserved and analyzed as described for the previous experiment. Influence ofpH on Perchlorate Biodegradation. An experiment was conducted lo determine whether the low pH (4-3) of the Hogout site samples was inhibiting perchlorate degradation at the site. Prior to adjusting the pH, the influence of increasing carbonate concentration on slurry pH was tested. The resulting titration curve showed that approximately 240 mg/L of additional caiixjnate was required to increase the pH of the slurry to 70 (Figure 13) Microcosms were piepared in sterile, 160-niL semm bottles- The groundwater was amended with a sterile stock of diammonium phosphate to provide nitrogen (1 mg/L NH4 as N) and phosphoms (1 mg/L PO4 as P) as nutrients for bacterial growth. Groundwater and sediment were added to each 160-nnL bottie at a ratio of approximately 3:1 (100-mL groundwater and 30-g sediment). Acetate was added as the electron donor at 75 mg/L. Perchlorate was not added, as the perchlorate concentration in the mixed groundwater and sediment was approximately 45 mg/L. In eight of the fourteen bottles prepared, the pH was increased from 4-3 to approximately 7-0 by adding sodium cart>onate. The pH of the remaining six microcosms was not adjusted (i e-, pH 4.3). Three of the bottles at pH 4.3 and three at pH 7 0 were inoculated with the perchlorate-degrading culture FBR2, and three bottles at each pH remained uninoculated. Two of the bottles at pH 7 0 received formaldehyde (1 %) to inhibit all biological activity The bottles were incubated on a rotary shaker at 15°C. After 7, 16, 28, and 44 days of incubation, a 7-mL subsample was removed from each bottle. Each sample was initially centrifuged for approximately 30 minutes at 3,500 rpm to remove sediment fines. The supernatant was then passed through a nylon filter and placed at 4°C until analysis. A freshly grown innocula of the FBR2 culture was re-added to three tx)ttles at each pH on Day 10. This procedure was conducted to ensure that all bottles amended with the bacterium received active perchlorate-degraders. Results: Groundwater Analysis: The groundwater collected from the Hogout site contained perchlorate al 25 mg/L In a slurry containing 30-g sediment and 100-mL groundwater perchlorate was detected at 45 mg/L suggesting that the anion was present at a higher concentration in the sediments collected from the 10 site than in the site water This diffeience may lepiesent perchloiate present in the unsaturated zone of the shallow aquifer. Nitrate and nitrite were not detected in samples. Sulfate was present at 88 mg/L, chloride at 26 mg/L, and alkalinity was 19 mg/L (as CO3) The pH of the water was 4 8, and a sluiry of water (100 mL) and sediment (.30 g) had a pH of 4.3. Electron Donor Addition: There was no appreciable loss of peichlorate during the 71-day incubation period in any ofthe microcosms piepared from the Hogout site samples (Table 2). Ten different electron donors did not stimulate perchlorate biodegradation in the samples. Bioaugmentation with an exogenous perchlorate-degrading enrichment (FBR2) also did not lead to reduced perchlorate levels These results differ from those with the Building 1170 samples, where several election donois quickly stimulated perchlorate degradation. Rapid reduction in perchlorate levels was also observed in aquifei microcosms from the Jet Propulsion Lab and a commercial site in the Rocky Mountains (see following section) The most apparent difference between the Hogout samples and those from other sites is the comparatively low pH of the microcosms compaied to othet samples. The pH of the Hogout site microcosms was measured at 4.3. Other samples tested thus far in this project have had pH values no lower than 6.1- An experiment was subsequently conducted to assess the influence of pH on peichlorate degradation in the Hogout samples. Influence of pH on Perchlorate Degradation: The perchlorate levels in the samples at pH 4 3 did not decline appreciably duiing the study, regardless of whether the samples were bioaugmented (Figure 14). Conversely, the samples in which the pH was increased to 7.0 all showed peichlorate biodegiadation. Perchlorate levels in samples receiving the FBR2 enrichment culture declined from 43 to 9 mg/L from day 7 to day 16, and then to 0.16 mg/L by day 28. The perchlorate concentration in samples that were brought to pH 7.0 but not augmented with the culture declined more slowly, but perchlorate was below detection by day 28 of the experiment. Thus, the data suggest lhat low pH is inhibiting perchloiate degradation in the Hogout site samples. It is interesting that indigenous perchloiate-degrading microorganisms could be stimulated to degrade the anion at a pH of 7.0 but not at a pH of 4 3 These bacteria are obviously able to survive at the low pH, which occurs naturally at this site, yet appear not to degrade perchloiate at this pH. The results suggest that there may be a pH below which perchlotate biodegradation is physiologically inhibited. Conclusions: Data from experiments conducted with samples from the Hogout site at IHDFV suggest that low pH is inhibitory to biological perchlorate reduction. Neidier biosdmulation nor bioaugmentation promoted peichlorate degradation at the site pH of 4.3. However, when the pH of the samples was increased to neutrality, perchloiate biodegradation was observed in samples receiving acetate as well as those augmented with the FBR2 enrichment culture. The inhibition of perchlorate degiadation at low pH in these field samples is consistent with previous obseivations at Envirogen during experiments with ex situ reactor systems. During a laboralory pilot study, perchlorate treatment in a fluidized bed reactor was observed to decline appreciably when the pH of the system declined below approximately 5.5. The performance was regained when the pH was increased to neutrality. Additional experiments are underway with pure cultures isolated at Envirogen to further define the influence of pH on perchlorate biodegradation. C. ROCKY MOUNTAIN COMMERCIAL FACILITY (RM). Sample Collection. Groundwater samples were collected by site personnel at an industrial manufacturing facility in the Rocky Mountains Sediment samples were not available 11 Microcosm Studies - Rockv Mountain Site. Methods: Groundwater Microcosms: Microcosms were used to evaluate the poientiai for perchlorate biodegradation in a subsurface aquifer in the Rocky Mountains. Subsurface sediments weie not available for this study, so groundwater only was used in the experiments. The Rocky Mountain gioundwater was amended with a sterile stock of diammonium phosphate to provide nitrogen (5 mg/L as NH,) and phosphoms (45 mg/L as P) as nutiients for bacterial growth. Each 160-mL bottle received 1(X) mL of site groundwater. The perchlotate concentration in the groundwater was approximately 57 mg/L. Duplicate semm bottles were amended with one of the following substrates to 100 mg/L: acetate, ethanol, methanol, benzoate, lactate, sucrose, molasses or a mixture of ethanol and yeast extract (100 mg/L each). Duplicate bottles also received hydrogen or propane in the headspace as gaseous substiates Duplicate bottles were inoculated with the perchlorate-degrading enrichment culture (FBR2) and ethanol as election donot. Duplicate samples were also prepared with nutrients (N and P) but no substrate, no nutrients or substrate, or substrate (acetate) without nutrients. Killed controls received acetate as substrate and formaldehyde (1 %) to inhibit all biological activity All bottles were ciimp-sealed with sterilized Teflon- lined septa and incubated at 15°C to approximate IH situ temperatures. At 6, 14, 22, and 35 days of incubation, a 15-ml subsample was removed ftom each bottle Preservation of the samples was accomplished by filtration and refrigeration, as described previously. Influence of Co-Contaminants: An expeiiment was conducted using groundwater from the RM site to assess the influence of co<ontaminants on perchlorate biodegradation. In this study, seium bottles were amended with lactate (100 mg/L), nutrients, and one of the following co<ontaminants at a starting concentration of 100 mg/L: perchloroethylene (PCE), trichloroethylene (TCE) oi the mixed gasoline constituents benzene, toluene, ethylbenzene, and xylenes (BTEX). The bottles were sealed and placed on a rotary shaker operaling at 15°C. Subsamples wete periodically collected and analyzed for perchloiate. Results: Groundwater Analysis: Groundwater from the Rocky Mountain site was collected ftom an existing monitoring well screened to a depth of 89 - 99 ft below giade. The water contained perchloiate at 57 mg/L, which is consistent with historical levels in the well- Other anion levels included nitiate at 52 mg/L (as N), sulfate at 364 mg/L, chloride at 2,500 mg/L, ahd 285 mg/L of alkalinity (as CaCOs). The total dissolved solids (TDS) in the gioundwater was 5,000 mg/L, and the pH was 7.7. Historical data provided lo Enviiogen by the commercial facility showed trichloroethene in the well water between 1 and 2 mg/L, and lesser chlorinated ethenes and ethanes at trace (ppb) levels. However, no volatile organic compounds wete detected in the gtoundwatei upon analysis by Envirogen's Analytical Lab These compounds were nrost likely volatilized during collection and shipment ofthe groundwater samples. The sampling techniques were designed to ensure aseptic collection of groundwater but not quantitative preservation of in situ VOC levels (since perchlorate is non-volatile) Groundwater Microcosms: The starting perchlorate concentration in microcosms prepared with groundwater was 57 mg/L. After 6 days of incubation at 15*'C, the perchlorate concentrations in samples augmented with exogenous perchloiate-degrading bacteria (culture FBR2) had decreased to 15 mg/L. Perchlorate levels did not decline in any of the olher treatments. After 14 days of incubation, perchloiate levels were below detection (MDL= 0.5 mg/L) in tbe FBR2-inoculated microcosms and in microcosms amended with sucrose, lactate, and molasses (Table 3). In microcosms amended with both ethanol and yeast extiact, peichlorate levels had decreased to 1 mg/L after 14 days, and were non-detect (MDL= 0.5 mg/L) after 22 days In microcosms receiving acetate, peichlorate levels declined to 31 mg/L after 14 days After 35 days, perchloiate levels in the acetate bottles were less than 0.3 mg/L. However, no perchlorate loss was obseived in microcosms prepared with acetate as electron donor but without nutrients (supplemental nitrogen and phosphoms), indicating that phosphoms may be a limiting nutrient 12 for microbial growth in the groundwater. Nitrogen is probably not limiting because high levels of nitrate are present in the water No perchlorate loss was observed in those microcosms amended with hydrogen, benzoate, ethanol, methanol, or propane as electron donors. No perchloiate loss was evident in samples that were treated with formaldehyde to inhibit biological activity, nor in samples that were piepared with nutrients only (no substrate) or those receiving no nutrient or substiate addition. Influence of Co-Comaminants. Peichlorate levels in samples that did not receive co-contaminants declined from 52.7 mg/L to 1.7 mg/L during the inttial 15 days of incubation and were below detection by day 29 (Figure 15). In samples that received TCE at 100 mg/L, perchlorate degradation was slightly retarded compared to the samples without the co-contaminant, but perchlorate was also below detection by day 29. Conversely, during the 29-day study, samples receiving either BTEX or PCE showed no degradation of perchlorate. Conclusions: Bioaugmentation with the FBR2 culture caused the most rapid reduction in perchlorate levels in the Rocky Mountain samples. However, addition of some substrates (lactate, molasses, sucrose, yeast extract/ethanol) also promoted perchlorate biodegradation by indigenous bacteria. Other substrates that yielded rapid perchlorate biodegradation at the IPL site or the IHDIV Building 1170 Site, such as ethanol (IPL) and hydrogen gas (IHDIV), did not stimulate biodegradation of the anion at this site Differences in the indigenous populations of perchloiate-degrading bacteria at each site may account for the observed differences among sites in substrate effectiveness for perchlorate bioremediation. The observed inhibition of perchloiate degradation by PCE and BTEX most likely reflects toxicity of these compounds on the perchlorate-degrading strains in the RM groundwater It is however, interesting that TCE appeared to be less toxic at 100 mg/L than PCE, since the foimer is more soluble and solvent toxicity often increases with solubility. An initial screening suggested that neitlier TCE or PCE were appreciably degraded during the course of the experiment. Additional studies are planned to evaluate the influence of PCE and TCE at lower concentrations on petchlorate degiadation. These studies are impoitant because chlorinated solvents, including PCE and TCE, are often found wilh perchlorate at contaminated field sites. Isolation and Identification of Perchlorate-degrading bacteria from FBRs and Field Sites. Methods: One objective of this project is to enrich and isolate consortia and pure cultures of perchlorate-degrading bacteria for use in microcosm and column studies (i.e., evaluation of bioaugmentation for perchlorate degiadation) as well as to letter understand variables influencing perchlorate degradation at the cellular level. Enrichment cultures were prepared from Envirogen bioreactors and fix)m subsurface samples collected at JPL, IHDFV, and the RM site. Samples were added to a phosphate-buffered enrichment medium containing ammonium chloride, numerous trace elements (Co, Mn, Cu, Al, etc), casamino acids (0.5 g/L) and yeast extiact (0.5 g/L) as sources of vitamins and other growth factors potentially required by the oiganisms. The isolation medium was amended with ammonium peichlorate to 1000 mg/L (CIO4) and ethanol 01 acetate (JPL enrichment) to 500 mg/L- The samples were incubated on a rotary shaker operating at 100 rpm and 30''C in the daik The bottles were periodically checked for signs of microbial growth (turbidity). Any samples showing turbidity were transfened to fresh, sterile media under anoxic conditions. To conduct a transfer, serum bottles weie opened using aseptic conditions in the anaerobic chamber, and a small volume ofthe media (0025 - 0050 mL) was pipetted to a semm bottle with fresh media. After several transfers, perchlorate levels were checked in bottles showing microbial giowth. and subsamples from each bottle showing perchlorate degradation were plated on two types of agar media. The liquid samples were plated on the R2A agar, (which is a simple medium designed for culturing groundwater bacteria), and incubated aerobically, as most perchlorate-degiading cultures are facultative anaerobes. Samples were also plated 13 on a solid agar medium containing the same constituents as the enrichment media plus 15 g of agar per liter. Individual colonies were selected from solid agar plates and streaked on fresh plates several times in succession until each appeared to be a pure culture. The cultures were then inoculated from plates into liquid media with perchlorate, and perchlorate degradation was tested. Cultures that reduced perchlorate were rechecked for purity, then identified using 16S rRNA gene analysis (Acculab Inc., Newark, DE). Results: Some of the samples collected from IHDFV showed microbial growth after several days of incubation and were transfened. A few of these samples again became tuibid after transfer, and were transferred one or two additional times. However, when levels of perchlorate were tested in the enrichments, none showed appreciable perchlorate degiadation. Thus, although some microbial growth is occuning in these samples, the bacteria do not appear lo be perchlorate-degiading strains. One pure culture was isolated fiom bioreactor samples initially collected fiom a fluidized bed bioreactor treating perchloiate in California (Figure 16). The pure culture, which was identified by 16S rRNA gene analysis as a Declilorospirillum sp-, was isolated from the enrichment culture that has been used for bioaugmentation in several ofthe miciocosm studies- The Dechlorospirillum sp (FBR2) is veiy similar to a bacterium (strain WD) isolated from swine waste by Dr. John Coates at Southem Illinois University (SIU). The two strains have a 0.4 % nucleotide difference. This appears to be the only other organism in the available 16S rDNA databases that has reasonable similarity to strain F6R2. In addition to strain FBR2, two pure cultures were isolated from aquifer samples collected from JPL These cultures were each identified at the species level as Dechlorisoma suilla. A photomicrograph of D siiilla IPLRND is given in Figure 17. A positive enrichment culture was also obtained from the RM gioundwater sample using lactate as a carbon source. The perchlotate degrading strain in this enrichment culture has not yet been purified and identified. All of these strains have been sent to Dr. Coates at SIU for further study and inclusion in his collection of perchlorate-degiading bacteria. Conclusions: The preliminaiy results of this project suggest that perchlorate-degiading bacteria are widely-occuning in the environment Pure cultures were isolated from gtoundwatei at the Jet Propulsion Laboratory and from Envirogen reactors (initially seeded with food processing waste) In addition, an enrichment culture was obtained from the Rocky Mountain Site. Although pure cultures were nol isolated from the IHDIV samples, laboratoiy results showed that perchlorate-degrading bacteria aie present at this site. The enrichment media used for culture isolation may not have been appiopiiate based on the physiology of the strains in this environment. Few studies exist regaiding the occunence and phylogeny of perchloiate- degrading bacteria in natural environments. However, the strains identified (Dechlorospirillum spp., Dechlorosoma spp.) are similar to bacteria recently discovered by Coates et al, (1999) in environmental samples. References Cited. Atlas, R. M. 1995 Handbook of Media for Environmental Microbiology CRC Press, Inc., New York Attaway, H., and M. Smith. 1993. Reduction of perchlorate by an anaerobic entichment culture. J. Ind Microbiol., 12:408-412 Breznak, J. A., and R. N. Costilow. 1994 Physicochemical factors in growth, pp. 137-153, In P C}erhardt (ed), Methods for General and Molecular Biology, American Society foi Microbiology, Washington, DC. Coates, J. D., U. Michaelidou, R. A. Bruce, S. M. O'Conncr, J. N. Crespi, and L. A. Achenbach. 1999. Ubiquity and diveisity of (per)chlorate-reducing bacteria. Appl Environ. Microbiol. 65:5234-5241. DeFlaun, M. F,, C. J. Murray, W. Hdben, T. Schiebe, A. Mills, T. GInn, T. Griffin, E. Majer, and J. L. Wilson. 1997 Preliminary observations on bacterial transport in a coastal plain aquifei FEMS Microbiol, Rev. 20:473-487 14 Jenneman, G. E., M. J. Mclnerney, and R. Knapp. 1986. Effect of nitrate on sulfide pioduction Appl. Environ. Microbiol., 51:1205-1211. Logan, B. E., 1998. A review of chlorate- and perchlorate-iespiring microorganisms Bioremediation Joumal, 2:69-79. Logan, B. E. and K. Kim. 1998. Microbiological treatment of perchlorate contaminated groundwaters pp 87-90, In Proceedings of the Southwest Focused Ground Water Conference: Discussing the Issue of MTBE and Perchlorate in Ground Water, National Ground Water Association, Analieim, CA. Mandalas, G. C, J. A. Christ, and M. N. Goitz. 1998. Screening software for an innovative in situ bioremediation technology. J. Bioremediation, 2:7-15. Manzon, R. G., and J. H. Youson. 1997. The effects of exogenous thyroxine (T4) or triiodothyioxine (T3), in the presence and absence of potassium perchlorate, on tfie incidence of metamorphosis and on semm T4 and T3 concenttations in larval sea lampreys (Petromyzon marimts L). Gen. Comp. Endocrinol-, 106:211-220 McCarty, P. L., M. N. Goltz, G. D. Hopkins, M. E. Dolan, J. P. Allan, B. T. Kawakami, and T. J. Carrothers. 1998. Full-scale evaluation of in situ cometabolic degradation of trichloroethylene in groundwater through toluene injection. Environ. Sci. Technol., 32:88-100. Rikken, G. B., A. G. M. Kroon, and C. G. van Ginkei. 1996. Tiansfoimalion of (per)chloiate into chloride by a newly isolated bacterium: reduction and dismutation. Appl. Microbiol Biotechnol 45:420-426. Saito, M., M. Scki, S. Amemiya, K. Yamasu, T. Suyemitsu, and K. Ishihara. 1998. Induction of metamorphosis in the sand dollar Peronella japonica by thyroid hormones. Dev. Growth Differ 40:307-312. Smith, R. L. 1997. Deteimining the terminal electron-accepting reaction in the saturated subsurface, p. 577-585. In C. J- Huist (ed). Manual of Environmental Microbiology.. ASM Press, Washington- Steffan, R. L., K. L. Sperry, M. T. Walsh, and C. W. Condee, 1999. Field-scale evaluation of in situ bioaugmentation for remediation of chloiinated solvents in groundwater Environ. Sci. Technol., (in press). Urbansky, E. T., 1998. Peichlorate chemistry: implications for analysis and remediation Bioremediation Journal, 2:81-95. U. S. Environmental Protection Agency. 1999. Perchlorate. Office of Giound Water and Drinking Water, Website: Worldwide Web: epa.gov/OGWDW/ccl/perchlor/perchlo.html, 13 pp. van Ginkei, C. G., A. G. M. Kroon, G. B. Rikken, and S. W. M. Kengen. 1998. Microbial conversion of petchlorate, chlorate, and chlorite, pp. 92-95.//1. Proceedings of the Southwest Focused Giound Water Confeience: Discussing the Issue of MTBE and Peichlorate in Giound Water, National Ground Watet Association, Anaheim, CA, Wallace, W., T. Ward, A. Breen, and H. Attaway. 1996. Identification of an anaerobic bacterium which reduces perchlorate and chlorate as Wolinella succinogenes. J. Ind. Microbiol., 16:68-72 Wolff, J. 1998. Perchlorate and the thyroid gland. Pharmacol. Rev, 50:89-105 15 V. TABLES Table 1. Perchlorate Degradation in JPL Sediment/Groundwater Microcosms Amended with Various Electron Donors or Perchlorate-Degrading Bacteria Treatment Electron Donors Killed Control Benzoate Methanol Hydrogen Propane No Addition Sucrose Ethanol Lactate Molasses Yeast Extract/Ethanol^ Acetate Bacteria Added Killed + Inoculum FBR2^ Inoculum FBR2+ YE/Etoh Inoculum FBR2-h Acetate Perchlorate Concentration (UK/L)' DayO 310±0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 310 + 0 Day 10 293 + 6 297 + 6 77 + 57 177 + 61 283 + 6 14+19 92 + 67 <5 <5 <5 <5 <5 Day 21 320 + 0 150+135 <5 <5 <5 <5 <5 NS^ NS NS NS NS 1 310±0 310±0 310±0 385 + 7 <5 <5 415 + 7 NS NS Values ore the mean + standard deviation from triplicate microcosms ^ NS = Not sampled because previous sample point was below detection ^ FBR2 is a perchlorate-degrading culture isolated at Envirogen 16 Table 2. Perchlorate Degradation in Sediment/Groundwater Microcosms from the IHDIV Hogout Site Treatment Electron Donors Killed Control No Substiate Nutrients Only Hydrogen Propane Ethanol Methanol Acetate Benzoate lactate Molasses Sucrose Yeast Extiact/Ethanol Bioaugmentation Inoculum FBR2-+ Etoh Perchlorate Concentration imtJh)' DayO 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42 + 4 42±4 42 + 4 42 + 4 Day 11 41 + 1 37+1 38 + 2 38 + 2 38+1 39 + 2 41 +2 39+1 40±1 38 + 3 43 + 2 44+1 43 + 2 41 + 1 Day 20 44±2 36 + 4 41+4 40 + 4 39 + 2 41+2 41 + 1 42 + 2 43 + 0 43 + 3 43 + 2 45+0 44±2 44 + 3 Dav 36 36 + 4 38±1 42+1 32 + 5 34±2 36 + 4 32±2 33 ±1 32+1 33 + 2 28±1 31+0 35±3 36 + 2 Day 71 37 + 2 39 + 5 34+1 35 + 2 37 + 2 36 + 3 34 + 2 37+1 38+1 37 + 2 36 + 2 35 + 0 37 + 2 36 + 2 ' Values arc the mean + standard deviation from triplicate microcosms ' F6R2 is a perchlorate-degrading bacterium isolated at Envirogen 17 Table 3. Perchlorate Degradation in Groundwater Microcosms from the Rocky Mountain Site Treatment Electron Donors Killed No Addition Nitrogen/Phosphorus only Hydrogen Propane Benzoate Ethanol Methanol Acetate (no N or P) Acetate Yeast Extract/Ethanol Lactate Molasses Sucrose Inoculum Added Culture FBR2 + Etoh I ,,:... _ .L _ _ . -r • Perchlorate Concentration (mg/L)' DayO 57 + 2 57 ±2 57±2 57 + 2 57 + 2 57 + 2 57±2 57 + 2 57 + 2 57 + 2 57 + 2 57 + 2 57 + 2 57 + 2 57 + 2 Day 6 60 + 2 60+1 62 + 5 61 + 1 62 + 0 62 + 2 59 + 3 62 + 2 60 + 5 62+1 60 + 0 60±1 59 ±1 61 + 1 15+1 Day 14 53±2 53 ±1 55 ±1 63+10 66 + 1 62+1 63 + 2 63 + 1 54 + 0 31+6 1 + 1 <0.5 <0.5 <0.5 <0.5 Day 22 60^ 53 ±2 59+1 52+1 49±0 49 + 3 51 ±0 46±4 59±1 2 + 2 <0.5 <0.5 <0.5 <0.5 <0.5 Day 35 55^ 54+ I 55 + 2 54+1 53 + 0 48 + 2 43+ 1 47 + 6 49+1 <0.5 NS^ NS NS NS NS ~ NS: Not sampled because perchlorate was previously below detection ^ Single analysis due to broken sample bottle 18 VI. FIGURES Figure L Photograph of Aquifer Microcosms '-.•--•JS:C:t.-.;."> :^m& m^^^^ Figure 2. Perchlorate Degradation in Groundwater Microcosms Amended with Various Electron Donors 350 300 250 200 i ^ 150 100 : 50 T 0 1~» -•- —.^— —•— Acetate Yeast Extract Methanol Molasses - No Addition - Killed -I 1 1 r 25 Figure 3. Degradation of Perchlorate (100 mg/L) and Nitrate (100 n^) in Aquifer Microcosms from JPL with Ethanol as a Substrate 140: 120 ( ) 1001 "O 80- A 60: 40: 20 . Oi ^ I \ Nitrate \ : \ : X \ Nitrite Av ft ' B 1 ill 1 ; • ^ -• i ' •• ' m ^ Perchtorate \ \ I \ ] ;\ • • n '^^ i ^N. • ^«B iHii|hiii|i^ii|iiBii 0 10 15 Days 20 25 30 Figure 4. InflueiKe of Nitrate (100 mg/L) on Perchlorate Biodegradation in Aquifer Microcosms from JPL 140 120 ) 100 •0 80 60 40 20 -1—I—I—I—I 1—I—I—I—I—I—1—r Nitrate Added (IOO ppm) No Nitrate Added Killed COntiol 1—I—1—1—I—I—I—I—I—I—I—|- 0 10 15 Days 20 25 30 20 Figure 5. Bk)degradation of Perchlorate (100 vagfL) and Nitrate (100 mg/L) in JPL Microcosms with No Substrate Added 120 100 n 9 -•— Perchlorate Hi— Nitrate -^— Nitrite 10 15 Days 20 25 Figure 6. Influence ofOxygen on Perchlorate Degradation in Aquifer Microcosms from JPL 21 400 250- 200 150 i 100 50i Figure 7. Influence of Salinity on Perchlorate Degradation in Aquifer Microcosms from JPL -•— 0.25 X Seawater Hi— 0.5 X Seawater -•— 1 X Seawater -•— Killed Q —j 1 1 1 1 1 1 1 1 1 j 1 1 1 1 1 1 1 1 1 1 r T—I 1 1 1 1 r- 10 15 Days 20 25 30 Figure 8. Influence of pH on Biodegradation of Perchlorate in Aquifer Samples from JPL 350 10 15 Time 20 25 30 22 Figure 9. Collection of Field Samples from the IHDIV Building 1170 Site Figure 10. Collection of Field Samples at the IHDIV Hogout Site 23 Figure 11. Influence of Electron Donors on Perchlorate Degradation in Aquifer Microcosms from IHDIV Building 1170 Site 150 "(1 10 15 20 Days 25 30 35 Figure 12. Influence of Electron Donor Concentration on Perchlorate Degradation in Aquifer Samples from IHDIV Buildhig 1170 Site 140 120 -X >< •-x;. 0.35 0.50 0.62 14 24 Figure 13. Carbonate Titration Ciure for Sediment Slurries fixim IHDIV Hogout Site 100 200 300 400 Carbonate Alkalinity (mg/L) 500 600 Figure 14. Influence of pH on Perchlorate Degradation in Aquifer Microcosms from the IHDIV Hogout Site -ffl—Killed -I 1 1 1 1 1 1 1 1 r 10 15 Days 20 25 30 25 Figure 15. Influence of Co-Contaminants on Biodegradation of Perchlorate in Groundwater from the Rocky Mountain Site 60 0 1—'—I 1—I—I—I—'—'—I—I—'—I—I I—I—I I I I I I I I ' I I I—r- 10 15 Days 20 25 30 Figure 16. Photomicrograph of DechlorospiriUiun sp. FBR2 after staining with Acridine Orange 26 Figure 17. Photomicrograph of Dechlorosoma suilla JPLRND after staining with Acridine Orange 27 APPENDIX A. PRESENTATIONS and PUBLICATIONS This research has been presented in platform sessions at two conferences. The conference citations are listed below. Hatzinger, Paul B. 2000. Biotreatmentof Perchlorate in Groundwater. Partners in Environmental Technology Symposium and Workshop. Arlington, VA. November 28 - 30,20(X)., pp. 38 Hatzinger, Paul B. 2000. In Situ Bioremediation of CIO4'in Groundwater. Fifth Annual Joint Services Pollution Prevention & Hazardous Waste Management Conference San Antonio, TX. August 21-24, 2000. 28 KLEINFELDER APPENDIX B Abbreviated Site Safety and Health Plan Pilot Test for well B-6 Promontory Facility Promontory, Utah KtEINFELDER INTRODUCTION This ASHP describes the measures that will be taken to ensure the protection of Kleinfelder and Zimmerman field personnel during the groundwater monitoring, sparge well installation, and pilot test system installation, operation, and disassembly. The site is located in Promontory, Utah as shown in Figure 1 in the work plan. The route to the nearest hospital, Bear River Valley Hospital, 440 West 600 North, Tremonton, Utah (435-257-7441) from the site can be navigated by: • Leave the site heading south on Highway 83 and travel 8 miles; • Tum left onto Highway 102 and travel 16 miles; • Tum left on N 400 W and travel 0.5 miles; and • Tum left on W 600 N and travel 0.1 miles to arrive at the hospital. This ASHP was prepared to address the work associated with the Pilot Test for Perchlorate Remediation. Commensurate with the scope of this project, this ASHP will incorporate the following tasks: • On-site Drilling Activities for the Sparge Well; Installation ofthe Sparge Well; Pilot Test Injection and Maintenance; and • Groundwater Observation Activities. • • KLEINFELDER 2. PERSONNEL AND RESPONSIBILITIES 2.1 TRAINING Subcontractors will be provided with a copy of this ASHP and must be reviewed before commencing fieldwork. A sign-up sheet has been provided in Attachment 1 for those who have reviewed and understand this ASHP. Subcontractors are required to comply with all applicable and appropriate federal, state, and local laws, standards, and regulations. Kleinfelder does not assume responsibility for the health and safety of subcontractor or otir client's employees. Explosives and other hazardous materials are handled at ATK - Promontory Facility; thus, site- specific safety precautions must be followed. General site-specific training (safety, quality, etc.) is done through the Promontory Training Department. To schedule this training prior to fieldwork, John Holladay shall be contacted at (435) 863-6895. Completion ofthis training will allow for subcontractor's to receive unescorted worksite pennits. 2.2 KEY PERSONNEL AND RESPONSIBILITIES Personnel associated with this ASHP include: Name Chris Busch John Holladay David Shank Jen Cowan Jim Grippa or Matt Ivers Company and Title ATK, Project Manager ATK, Geologist Kleinfelder, Quality Control Manager Kleinfelder, Project Manager Kleinfelder Field Leader / Site Safety and Health Officer Mike Zimmerman Zimmerman Well Services, LLC Rich Bohrer Kleinfelder, CIH (off site) Phone (801)251-3562 (435) 863-6895 (801)261-3336 (801)261-3336 (801)243-7341 (801)250-1400 (916)366-1701 Responsibilities Project oversight Site and training contact Work plan review Document author Direct field work, construct pilot test system, oversee site safety Well driller ASHP review and authorizes changes KLEINFELDER 2.3 SCHEDULE Kleinfelder employees will be on site during well drilling, pilot test system constmction/maintenance, and for a portion of the groundwater sampling activities to observe ATK's protocols and equipment. The schedule for these activities is shown in Figure 4 of the work plan. Kleinfelder will not be responsible for safety and health concems during groundwater sampling or of ATK and subcontractors employees. KLEINFELDER 3. SITE CONTROL AND COMMUNICATION 3.1 SITE ACCESS Once the site-specific training has been completed, subcontractors will be able to enter and leave the site without an escort. Persormel entering the Promontory Facility may not bring the following items (contraband) through the gate or doors: • Illegal or unauthorized dmgs; • Alcoholic beverages; • Firearms and other lethal weapons (e.g., tear gas, stun gims, etc.) beyond a controlled entry point; • Video and still cameras, unless accompanied by an ATK Thiokol Inc. camera pass issued by the appropriate facility; or • Pornography. 3.2 VEHICLE AND SECURITY PROCEDURES ATK has many vehicles whose primary purpose is to transport explosives in various forms. There is a high probability of encountering vehicles with flashing lights while traveling on-site. The following rules must be adhered to as part of ATK's policies. KLEINFELDER 3.2.1 Encountering Other Vehicles If you meet any vehicle that displays a flashing red light, you must pull your vehicle off to the right side ofthe road 100 feet before meeting the vehicle until it has passed. If you approach such a vehicle from the rear, you must follow at a minimum distance of 100 feet. These vehicles will be carrying hazardous materials or explosives, or will be responding to an emergency (ambulances and fire tmcks). When in doubt, pull over and stop. Under no conditions should you pass any forklift from either direction, whether loaded or unloaded. If you meet any forklift, you must pull your vehicle off to the right side of the road 100 feet before meeting the forklift and let it pass. If you approach a forklift from the rear, you must follow at a minimum distance of 100 feet. 3.2.2 Vehicle Use ATK requires the use of seat belts by all personnel in a moving vehicle while on-site. The speed limit on Promontory plant roads is 25 miles per hour, unless posted otherwise. Always follow the posted speed limit. Park your vehicle only in designated locations. At operating buildings, you must park beyond the yellow-and-white parking triangles (50 feet from buildings). When parking your vehicle, make sure that it does not block egress from any building, other vehicle traffic, or access to the building by emergency crews. You may pull up to the building only to load or unload heavy materials or equipment. Parking Triangle KLEINFELDER Occasionally a road may be barricaded because of hazardous work being perfonned within an area. In the event this happens, use altemate routes. Do not drive through or otherwise enter barricaded areas. A flashing blue light indicates designated explosive operations that are perfonned remotely (unattended). Lights are positioned and a sign is posted on the roadside indicating the beginning ofthe Quantity/Distance (Q/D) circle (mandated distance from explosive operations) surrounding the building performing the remote explosive operation. When the light is flashing, you are not allowed to stop your vehicle within this Q/D circle. A flashing red light on a building indicates that a hazardous operation is in progress. Do not stop next to or enter these buildings. Personnel must stop at the entrance gate and show their badge to the security guard, or use the automated badge-scaiming device when a guard is not present. If you use the badge-scanning device, you must wait unfil the gate closes before pulling away. Allowing other vehicles to pass through the gate using your badge scan is a violation of Security procedures. 3.3 BUDDY SYSTEM The Buddy System includes maintaining two-way radio or cellular telephone contact with ofF-site personnel and/or visual contact with other personnel located on-site. Hand signals that will be used in an emergency situation where verbal communication is ineffective are: • Gripping throat, "Out of air; Can't breathe"; • Grip partner's wrist or both hands around waist, "Leave area immediately"; • Hands on top of head, "Need assistance"; • Thumbs up, "OK; 1 am alright; I understand"; or KLEINFELDER • Thumbs down, "No; Negative". 3.4 NO SMOKEMG ATK policy prohibits smoking in any building and in hazardous locations (generally within the inner-fenced plant area). You must go to a designated smoking area to smoke. Cigarette and cigar butts are to be extinguished and deposited only in ashtrays or butt cans in approved locations. Do not deposit trash in ashtrays or butt cans, as this can lead to a fire. Do not use the vehicle cigarette lighter or smoke inside a vehicle inside the fenced plant. KLEINFELDER HAZARDS 4.1 SITE-SPECIFIC HAZARD SYMBOLS There are three symbols in use at the Promontory Facility to indicate fire hazards and firefighting protocol for explosive materials. a. Symbol 1 (Class 1.1 explosives) is posted on buildings and vehicles containing energetic materials classified as a mass detonation hazard. In case ofa fire, DO NOT FIGHT THE FIRE in these buildings or vehicles. If possible and safe to do so, activate the building or vehicle fire extinguishing system(s). Evacuate to a distance of at least 2,000 feet, or as directed by supervision. b. Symbol 3 (Class 1.3 explosives) is used on buildings and vehicles containing explosives classified as a mass fire hazard. In case of a fire, activate building or vehicle fire extinguishing system(s) as applicable. Do not fight the fire unless the fire is minor, does not involve explosives, and appears controllable. c. Symbol 4 (Class 1.4 explosives) is used on buildings and vehicles containing materials classified as a moderate fire hazard. In case of fire, this type of fire may be KLEINFELDER fought if safe to do so. Portable and mobile fire extinguishing equipment can be used until the fire has been brought under control. WARNING: Some chemicals may emit toxic vapors in a fire; so do not attempt to fight the fire and allow others with the proper training to do so. 4.2 CHEMICAL HAZARDS Data from Material Safety Data Sheets (MSDSs) have been utilized in evaluating the chemical hazards described in Table B-l. Based on these hazard analyses, there are potential chemical hazards associated with this project. To mitigate these potential hazards, personal protective equipment must be utilized to protect workers. MSDSs for chemicals associated with this pilot test are included in Attachment 2. The main contaminant of concem in the groundwater is perchlorate. Concentrations of perchlorate exceed the Interim Action Level established for Califomia of 4 Jig/L (a level has not yet been established for Utah). Perchlorate originates from the solid salts of potassium, ammonia, and sodium perchlorate. Perchlorate is an oxidizer and in pure form should not be stored with flammable or combustible materials. Thermal decomposition ofthe perchlorate salts may release toxic frames. Ethyl acetate is a colorless liquid with a strong fhiity odor and is highly flammable. Inhalation of this product should be avoided when handling. Personnel will position themselves upwind from the product to avoid frames and wear a full-face shield to guard against splashing. To transfer the liquid from the 5-gallon pails to the diffusion vessel, a peristaltic pump or similar method will be Kl KLEINFELDER used to minimize splashing and lifting. The containers will be bonded or grounded to prevent the build up of static electricity that could cause the ethyl acetate to ignite. If needed, a respirator with organic vapor cartridges may be wom; however, it is anticipated that a frill face shield will be sufficient. Chemical resistant gloves like Silver Shield® (4H) or PVA''"'^ (disposable nitrile gloves are insufficient) and a Saranex disposable suit are recommended to be wom to avoid chemical exposure or contact with the skin or body. Spills or leaks should be addressed by first immediately eliminating all ignition sources. Leaks may be absorbed with a vapor suppressing foam, and spills covered with dry earth, sand, or other non-combustible material and transferred into containers. Compressed nitrogen will be supplied by Praxair from a supply tank mounted on a trailer. Although nitrogen is non-toxic and does not require personal protective equipment, it should be recognized that it could act as an asphyxiant by displacing the necessary amount of oxygen to sustain a person's breathing. Nitrogen is a colorless, odorless, and tasteless gas. If a leak from the nitrogen tank is discovered, personnel will place themselves up-wind or away from the tank where fresh air is available. Emergency contact infonnation regarding nitrogen issues will be posted on the side ofthe nitrogen tank. Sodium TMP will be used for the application of the nutrient amendment and comes as a dry powder. This substance is used as a food and cleaning ingredient and is not toxic. Inhalafion or contact with skin and eyes should be avoided; however, serious health effects are not anticipated in these situations. In the case ofa spill, sweep or sweep majority of spill and flush residual spill area with water. 4.3 PHYSICAL HAZARDS During installation of the sparge well, physical heizards will exist from drilling operations with the drill rig. All on-site personnel should be familiar with the emergency shut-off for the drill rig. Steel-toed boots must be wom within 50 feet ofthe drill rig. Be aware of overhead hazards when raising the mast ofthe drill rig. During drilling and well constmction activities, the on-site KLEINFELDER Kleinfelder personnel will restrict access to the area so that only trained personnel are in the vicinity ofthe drilling equipment. Additionally, hearing protection (muff or plugs) to protect hearing will be wom while the drill rig is in operation. The protection device must have a noise reduction rating capable of providing the wearer with enough protection to reduce the received noise level to be below 85 dB A- weighed (A) scale. 4.4 BIOLOGICAL HAZARDS Potential biological hazards at the site include exposure to animals such as mammals, snakes, ticks, spiders, and rodents. Other mammals such as ground squirrels, rabbits, rats, and chipmunks should be avoided for other diseases such as the bubonic plague, fleas, and bites that could transmit rabies or other infections. First-aid for a rattlesnake bite consists of calming the victim, washing the affected area with soap and water, applying a cold wet cloth over the bite area, and immediately transferring the victim to the nearest hospital. Bite signs and symptoms include swelling, pain, bleeding at the site of bite, nausea, vomifing, sweating, chills, dizziness, weakness, numbness or tingling of the mouth and tongue, and changes in heart rate and blood pressure. Ticks are also found in this area and are most common during the early summer months. The major hazards associated with tick bites are infection and possible transmission of Lyme disease. Precautions include use of PPE, keeping legs and ankles covered, and following good personal hygiene techniques. If bitten, the tick should be removed by grasping the head with a pair of tweezers and pulling using a straight-out motion. Early signs and symptoms of Lyme disease generally include flu-like fever, persistent headache, chronic fatigue, and usually a red "ring" around the area of the tick bite. Medical attention should be sought immediately upon the onset of these symptoms. If immediately treated by a physician, most individuals recover fully in a short period of time. If not treated, more serious symptoms can occur. KLEINFELDER Although uncommon, hantavims has been found in Utah. The vims gains entry into the body via inhalation of particles from infected deer mice feces, urine, and saliva. Hantavims may infect the respiratory tract and is frequently fatal. Precautions include disinfection of work areas where mice are present, avoid contact or disturbance, use of PPE, and following good personal hygiene techniques. Any employee who experiences a respiratory disease within 45 days after a potential exposure should see a physician. Other symptoms include fatigue, fever, and muscle aches, especially in the large muscle groups (thighs, hips, back, and sometimes shoulders). 4.5 HEAT STRESS/COLD STRESS Wearing PPE can significantly increase risk of personnel developing heat stress, which can result in health effects ranging from transient heat fatigue to serious illness or death. Heat stress is caused by a number of interacting factors, including environmental conditions, clothing, workload, and the individual characteristics ofthe person. Because heat stress is probably one of the most common (and potenfially serious) illnesses at hazardous waste sites, personal awareness and other preventive precautions are vital. Fluids must be replenished adequately, and heart rate and body temperature monitored. The signs and symptoms indicating heat stress are as follows: • Heat rash: resulting from continuous exposure to heat or humid air; • • Heat cramps: caused by heavy sweating with inadequate electrolyte replacement. Signs and symptoms include: Muscle spasms; and Pain in the hands, feet, and abdomen. Heat exhaustion: occurring from increased stress on various body organs including inadequate blood circulation due to cardiovascular insufficiency or dehydration. Signs and symptoms include: Pale, cool, moist skin; Heavy sweating; KLEINFELDER Dizziness; Nausea; or Fainting. • Heat stroke: most serious form of heat stress. Temperature regulation fails and the body tempyerature rises to critical levels. Immediate action must be taken to cool the body before serious injury and death occur. Competent medical help must be obtained. Signs and symptoms are: Red, hot usually dry skin; Lack ofor reduced perspiration; - Nausea; Dizziness and confusion; Strong, rapid pulse; or Coma. Should an employee exhibit one or more ofthese symptoms, the employee will immediately stop work, find a shaded area or move to a cooled building, and drinking fluids until their body temperature is not in excess of 100 degrees Fahrenheit. Cold stress is not anticipated for this project, as fieldwork will commence during the summer months. KLEINFELDER PERSONAL PROTECTIVE EQUIPMENT The levels of personal protection required for each task are assumed to be Level D. Level D protective equipment shall consist ofthe following: • Nitrile gloves will be wom while handling saturate soil cuttings from the boring, as they will likely be impacted with concenfrations of perchlorate up to 42 mg/L. • Gloves will also be wom while handling the sodium TMP. • Steel-toed safety shoes or boots (leather, PVC, and/or mbber) meeting the specifications of American National Standard Insfitule (ANSI) Z41. • Hard hat while overhead hazards exist (i.e., drilling); all approved hard hats must meet the specifications of ANSI Z89.1. • Hearing protection (muff or plugs), as necessary. The protection device must have a noise reduction rating capable of providing the wearer with enough protection to reduce the received noise level to be below 85 dB (A). • Specifically when handling the liquid ethyl acetate, the work outfit will specifically include the following additional items: Full-face shield; Disposable Saranex suit; and Silver Shield® or PVA gloves with a higher degree of chemical resistance will be wom for this project while in possible contact with liquid ethyl acetate (nitrile gloves will not provide adequate skin protection). KLEINFELDER Although not required, PPE may be upgraded to Level C if determined necessary while handling the ethyl acetate. Level C PPE requires a fiill-face respirator with organic vapor cartridges to be wom in addition to the required Level D items listed above. Employees will have been previously certified fit-tested with the appropriate respirator before doiming at the Site. KLEINFELDER 6. EMERGENCY RESPONSE Emergencies should be immediately reported to the project manager and ATK personnel. Emergency response contacts are as follows: Name Fire, Police, Ambulance Poison Control Center Site Heath and Safety Officer - Kleinfelder Jim Grippa Client Representatives - ATK John Holladay Chris Busch Project Managers - Kleinfelder Jen Cowan David Shank CIH-Kleinfelder Rich Bohrer Nearest Hospital (see Figure I) Bear River Valley IHC Hospital 440 West 600 North Tremonton, UT Contact Number 911 800-764-7661 801-243-7341 435-863-6895 801-251-3562 801-261-3336 801-971-8541 (916)366-1701 435-257-7441 Emergency response equipment that should be kept onsite during field activities include: • Fire Extinguisher - note to be used in the appropriate application according to the MSDS sheets for project related chemicals • First Aid Kit KLEINFELDER • Communication o Verbal o Cellular o Hand signals Table B-l Chemical Hazard Analysis Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility Analyte Ammonium Perchlorate Ethyl Acetate Nitrogen Sodium TMP PEL NE 400 ppm (Note: Odor threshold is at 6-50 ppm) NE I5mg/m3* IDLH NE 2,000 ppm NE NE Deicription Is an oxidizer and used in manufacturing ot" rockei motors Clear, colorless liquid with strong fruity odor Not toxic, but can act as asphyxiant by displacing necessary oxygen to sustain life Non-toxic anhydrous white powder ExpoiurePathwayi Inhalation, reactivity, skin absorption Inhalation, reactivity, skin absorption Inhalation Inhalation, skin absorption Signs and Symptomt May cause bums to skin and eyes. Fire may produce irritating or poisonous gases. Defatting, drying, mildly irritating, headache, dizzyness, drowsiness, intoxication; long-term exposure may cause livcT and kidney damage Dizzyness, nausea, vomiting, diminished mental alertness, loss of consciousness, death May cause some irritation to body in some individuals; inhalation may cause sneezing or coughing. Expected concentrations 42 mg/L (dissolved in groundwater) 100% (non-diluted) 100% (non-diluted) 100% powder (approximately 20% diluted in water) PPE Rubber gloves; avoid skin contact; safety glasses Barricade, Responder, or Trellchem gloves; safety glasses; full-face respirator with organic vapor cannister Adequate ventilation for breathing as it displaces oxygen Gloves; avoid inhalation or contact with eyes Note: PEL - Permissible Exposure Limit IDLH - Immediately Dangerous to Life and Health Concentrations NE - Not established TMP - Trimetaphosphate • No specific exposure limits set by OSHA PEL; considered particulate not otherwise regulated or classified. Source: NIOSH website(http://www.cdc.gov/niosh/idlh/intridl4.htnil) ATK/5I27X.OOI/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page I of 1 June 22, 2005 KLEINFELDER Attachment 1 KLEINFELDER ONSITE SAFETY MEETING ATTENDEES I have read, understand, and agree with the information set for in this ASHP. I have also attended ATK's on-site training. I agree to perform my work in accordance with this ASHP. Signature Name (Printed)/Title Date KLEINFELDER Attachment 2 MSDSs 1/20/05 .ORN I. Ll. I Material Safety Data Sheets I Division of Facilities Services DOD Hazardous Material Information (ANSI Format) For Cornell University Convenience Only AMMONIUM PERCHLORATE Section 1 - Product and Company Identification Section 2 - Compositon/lnfonnation on Ingredients Section 3 - Hazards Identification Includinc Emergency Ovcr\'ie\v Section. 4 - First-Aid Measures Section 5 - Fire Fighting Measures Section 6 - Accidental Release Measures Section 7 - Handling and Storage Section 8 - Exposure Controls & Personal Protection Section 9 - Physical & Chemical Properties Section 10 - Stabilit\' & Rcactivitv Data Section 11 - Toxicological Infonnation Section 12 - Ecological Infonnation Section 13 - Disposal Considerations Section 14 - MSDS Transport Infonnation Section 15 - Reuulatoi-v Infomiation Section 16 - Other Infomiation ^'le information in this document is compiled from information maintained by the United States Department of Defense )0D). Anyone using this information is solely reponsible for the accuracy and applicability ofthis information to a particular use or situation. •^omell University does not in any way warrant or imply the applicability, viability or use ofthis information to any ;rson or for use in any situation. Section 1 - Product and Company Identification AMMONIUM PERCHLORATE Product Identification: AMMONIUM PERCHLORATE Jte of MSDS: 01/01/1985 Technical Review Date: 08/14/1979 FSC: 6810 NIIN: 00-628-3388 Submitter: D DG atus Code: C viFN: 01 Article: N it Part: N Manufacturer's Information Wanufacturer's Name: NAVAL ORDNANCE SYSTEMS COMMAND Manufacturer's Address I: anufacturer's Address2: N/P, NK OOOOO Manufacturer's Country: NK 1/20/05 i^neral Information Telephone: Tilmergency Telephone: N/P Emergency Telephone: N/P 1SDS Preparer's Name: N/P Troprietary: N Reviewed: Y ubiished: Y ^"AGE: JO003 Special Project Code: N lem Name: ^em Manager: Specification Number: NK ype/Grade/Class: NK -onit of Issue: Unit of Issue Quantity: ype of Container: Item Description Contractor Information contractor's Name: HOECHST CELANESE CHEM GROUP Contractor's Address I: UNKNOWN ontractor's Address2: DALLAS, TX 75356-9320 contractor's Telephone: 214-689-4000 Contractor's CAGE: 10001 Contractor Information •ontractor's Name: NAVAL ORDNANCE STATION contractor's Address!: 101 STRAUSS AVE Contractor's Address!: INDIAN HEAD, MD 20640-5000 ontractor's Telephone: 301-743-4659 contractor's CAGE: JO003 Section 2 - Compositon/Information on Ingredients AMMONIUM PERCHLORATE " igredient Name: AMMONIUM PERCHLORATE _igredient CAS Number: 7790-98-9 Ingredient CAS Code: M RTECS Number: SC7520000 RTECS Code: M WT: =WT Code: _Volume: =Volume Code: >WT: >WT Code: Volume: >Volume Code: _WT: <WT Code: <Volume: <Volume Code: " > Low WT: % Low WT Code: . High WT: % High WT Code: % Low Volume: % Low Volume Code: " J High Volume: % High Volume Code: _>Text: 100 % Enviromental Weight: ttp://msds.ehs.comell.edu/msds/msdsdod/a67/m33375.htm 1/20/05 )ther REC Limits: N/P ^SHA PEL: N/P OSHA PEL Code: OSHA STEL: OSHA STEL Code: vCGIH TLV: UNKNOWN ACGIH TLV Code: M T=iCGIH STEL: N/P ACGIH STEL Code: EPA Reporting Quantity: >OT Reporting Quantity: ^zone Depleting Chemical: N Section 3 - Hazards Identification, Including Emergency Overview AMMONIUM PERCHLORATE Jealth Hazards Acute & Chronic: N/P igns & Symptoms of Overexposure: _tAY CAUSE BURNS TO SKIN & EYES.FIRE MAY PRODUCE IRRITATING OR POISONOUS GASES. ~ ledical Conditions Aggravated by Exposure: J/P ',D50 LCSO Mixture: N/P Route of Entry Indicators: Inhalation: N/P Skin: N/P Ingestion: N/P _'arcenogenicity Indicators NTP: N/P lARC: N/P OSHA: N/P Carcinogenicity Explanation: N/P Section 4 - First Aid Measures AMMONIUM PERCHLORATE First Aid: 'RRIGATE THE CONTAMINATED EYES W/RUNNING WATER FOR 15 MINUTE OR LONGER,FOLLOWED BY PTHAMOLOGICAL TREATMENT.REMOVE CONTAMINATED CLOTHING & SHOES. Section 5 - Fire Fighting Measures AMMONIUM PERCHLORATE Fire Fighting Procedures: 'RAY WATE FROM BEHIND PROTECTIVE BOARD,IN ADV.STAGE-REFUGE crnusual Fire or Explosion Hazard: MAY IGNITE COMBUSTIBLES.MIXTURES W/FUELS MAY EXPLODE.RUNOFF TO SEWER MAY CREATE RE OR EXPLOSION. EiXtinguishing Media: DRY CHEMlCAL,CO*2 FOR SML FIRES.LG FIRES:FLOOD WAV ATER ash Point: Flash Point Text: N.A. \utoignition Temperature: _1p://msds.ehs.comell.edu/msds/msdsdod/a67/m33375.htm 1/20/05 Autoignition Temperature Text: N/A Lower Limit(s): Upper Limit(s): Section 6 - Accidental Release Measures AMMONIUM PERCHLORATE Spill Release Procedures: OVER WITH WEAK REDUCING AGENTS SUCH AS HYPO,BISULFITES OR FERROUS SALTS.BISULFITES -JR FERROUS SALTS NEED ADDITIONAL PROMOTER OF SOME 3M-H*2SO*4 TO ACCELERATE REACTION.TRANSFER THE SLURRY INTO A LARGE CONT. OF WATER NEUTRALIZE W/SODA ASH. Section 7 - Handling and Storage AMMONIUM PERCHLORATE _(andling and Storage Precautions: •^ther Precautions: Section 8 - Exposure Controls & Personal Protection AMMONIUM PERCHLORATE Repiratory Protection: ELF-CONTAINED BREATHING APPARATUS,AND/OR DUST MASK ventilation: AS REQUIRED TO CONTROL DUST IN AIR rotective Gloves: KUBBER Eye Protection: SAFETY GOGGLES >ther Protective Equipment: COVERALLS,FACE SHIELD,BODY SHIELD Work Hygenic Practices: N/P Supplemental Health & Safety Information: CONTAINER MAY EXPLODE IN HEAT OF FIRE.MAY EXPLODE ROM FRICT10N,SH0CK,HEAT OR CONTAMINATION.KEEP FIRE-EXPOSED CONTAINERS COOL WITH »v^ATER SPRAY TO PROTECT AGAINST EXPLOSION Section 9 - Physical & Chemical Properties AMMONIUM PERCHLORATE CC:D1 _RC/State License Number: Net Property Weight for Ammo: oiUng Point: Boiling Point Text: DECOMP.266F Jelting/Freezing Point: Melting/Freezing Text: N/A Decomposition Point: Decomposition Text: N/A apor Pressure: N/P Vapor Density: N/P __2rcent Volatile Organic Content: Specific Gravity: 1.95 olatile Organic Content Pounds per Gallon: ^,H: N/P Volatile Organic Content Grams per Liter: ' "iscosity: N/P _vaporation Weight and Reference: N/P Solubility in Water: APPRECIABLE _1p://msds.ehs.comen.edu/msds/msdsdod/a67/m33375.htm 1/20/05 vppearance and Odor: COLORLESS,ODORLESS CRYSTALS. T'ercent Volatiles by Volume: N/P Corrosion Rate: N/P Section 10 - StabiUty & Reactivity DaU AMMONIUM PERCHLORATE _^ability Indicator: YES Materials to Avoid: OWDERED METALS,IGNITION SOURCES,ORG MATLS,STRONG ACIDS stability Condition to Avoid: N/P "lazardous Decomposition Products: J/P Hazardous Polymerization Indicator: NO "Conditions to Avoid Polymerization: yp Section 11 - Toxicological Information AMMONIUM PERCHLORATE Toxicological Information: /P Section 12 - Ecological Information AMMONIUM PERCHLORATE Ecological Information: /P Section 13 - Disposal Considerations AMMONIUM PERCHLORATE Waste Disposal Methods: SE VAST VOLUME OF CONC.SOLUTION OF REDUCING AGENT(BISULFITES OR FERROUS SALTS W/3M- _*2SO*4 OR HYPO).NEUTRALIZE WITH SODA ASH OR DILUTE HCL.DRAIN INTO AN APPROVED DISPOSAL AREA WITH ABUNDANT WATER. Section 14 - MSDS Transport Information AMMONIUM PERCHLORATE ransport Information: N/P Section 15 - Regulatory Information AMMONIUM PERCHLORATE ; \.RA Title III Information: rv/P Federal Regulatory Information: 'P isiBte Regulatory Information: N/P Section 16 - Other Information AMMONIUM PERCHLORATE tp://msds.ehs.comell.edu/msds/msdsdod/a67/m33375.htm 1/20/05 ^ther Information: N/P HMIS Transportation Informatioii product Identification: AMMONIUM PERCHLORATE Transporation ID Number: 80266 :esponsible Party CAGE: JO003 ^ate MSDS Prepared: 01/01/1985 Date MSDS Reviewed: 08/14/1979 IFN: 08/14/1979 _ubmitter: D DG Status Code: C Container Information Unit of Issue: Container Quantity: _ Type of Container: Net Unit Weight: -rticle without MSDS: N Technical Entry NOS Shipping Number: adioactivity: _orm: Net Explosive Weight: oast Guard Ammunition Code: _lagnetism: N/P AF MMAC Code: ~OD Exemption Number: limited Quantity Indicator: Multiple Kit Number: 0 ' 'it Indicator: N _it Part Indicator: N Review Indicator: Y ' dditional Data: Department of Transportation Information OT Proper Shipping Name: AMMONIUM PERCHLORATE DOT PSN Code: ASH "^-'mbols: I OT PSN Modifier: Hazard Class: I.ID ''N ID Number: UN0402 i OT Packaging Group: II Label: EXPLOSIVE IID ^^ecial Provision(s): 107 ' ickaging Exception: NONE !Ton Bulk Packaging: 62 ''•ilk Packaging: NONE aximimum Quanity in Passenger Area: FORBIDDEN Vlaximimum Quanity in Cargo Area: FORBIDDEN •^*ow in Vessel Requirements: B I jquirements Water/Sp/Other: 1E,5E,19E ~ IMO Detail Information I tp://msds.ehs.comell.edu/msds/msdsdod/a67/m33375.htm 1/20/05 MO Proper Shipping Name: AMMONIUM PERCHLORATE TMO PSN Code: AZZ IMO PSN Modifier: MDG Page Number: 5126 TJN Number: 1442 UN Hazard Class: 5.1 MO Packaging Group: II -subsidiary Risk Label: - EMS Number: 5.1-09 fedical First Aid Guide Number: 745 — lATA Detail Information lATA Proper Shipping Name: AMMONIUM PERCHLORATE \TA PSN Code: BQC -rATA PSN Modifier: L\TA UN Id Number: 1442 \TA UN Class: 5.1 subsidiary Risk Class: UN Packaging Group: II \TA Label: OXIDIZER .packaging Note for Passengers: 509 Maximum Quantity for Passengers: 5KG ackaging Note for Cargo: 512 —laximum Quantity for Cargo: 25KG Exceptions: A22 AFI Detail Information _FI Proper Shipping Name: AMMONIUM PERCHLORATE AFI Symbols: .FI PSN Code: BQH _ FI PSN Modifier: AFI UN Id Number: UN0402 FI Hazard Class: I.ID _FI Packing Group: II AFI Label: "pecial Provisions: P4, 107 _ack Pack Reference: A5.8 HAZCOM Label Information "roduct Identification: AMMONIUM PERCHLORATE AGE: JO003 Assigned Individual: Y ^ompany Name: NAVAL ORDNANCE STATION _ompany PO Box: Company Street Address 1: 101 STRAUSS AVE ^ompany Street Address2: INDIAN HEAD, MD 20640-5000 US ealth Emergency Telephone: Label Required Indicator: Y •^ate Label Reviewed: 12/16/1998 ;atus Code: C Manufacturer's Label Number: '^ate of Label: 12/16/1998 ear Procured: N/K Organization Code: G '^hronic Hazard Indicator: N/P ve Protection Indicator: N/P Skin Protection Indicator: N/P _:tp://msds.ehs.comel[.eduymsds/msdsdod/a67/m33375.htm 1/20/05 tespiratory Protection Indicator: N/P Taignal Word: N/P Health Hazard: Contact Hazard: Vire Hazard: Reactivity Hazard: .^7/2002 11:47:48 PM tp://msds.ehs. comel 1 .edu/msds/msdsdod/a67/m3 3 3 75 .htm Comet Chemical Company Ltd. 3463 Thomas Street Innisni ,ON L9S 3W4 Te«: (705) 436-5580 Fax: (705) 436-7194 COMET Materials Safety Data - ETHYL ACETATE Shipping Name Transport of Dangerous Goods Class WHMIS Class Material Use 1. HAZARDOUS INGREDIENTS Ethyl Acetate CAS NUMBER 141-78-6 100% UN- 1173 ETHYL ACETATE Class 3; Pacldng Group II B2;D2B solvent; pharmaceutical mfg. synthetic flavours TWAEV (ppm) 400 LDi* ORAL 4100 (mg/kg) SKIN 18,000 LCs* ppm INHALATION 12,500 PHYSICAL CHARACTERISTICS Odour & Appearance Odour Threshold Vapour Pressure Vapour Density (air = 1) Boiling Point Freezing Point Specific Gravity Water Solubility 3. clear, colourless, liquid with strong fruity odour 6- 50 ppm - detectable well below TWAEV 73 mmHg (20°C) 3 77T -84°C 0.902 slight - 9% (20"C) FLAMMABILITY & REACIIVITY Flash Point Autoignition Temperature Flammable Limits Hazardous Combustion Products Firefighting Precautions Sensitivity to Static Discharge Sensitivity to Mechanical Impact Chemical Stability Reactive With Dangerous Decomposition Products -4°C 426°C 2% - 11% carbon monoxide, nitrogen oxides, smoke foam, dry chemical, water fog, water spray only to cool, product floats on water - water jet spreads flames; firefighters must wear SCBA not sensitive not sensitive stable; will not polymerize strong oxidising agents; strong acids or alkalies, chlorosulphonic acid, potassium tert-butoxide, and oleum none apart from "Hazardous Combustion Products" 4. TOXICOLOGY EFFECTS OF ACUTE EXPOSURE Skin Contact defatting, drying, mildly irritating Skin Absorption yes; but toxic effects unlikely by this route (see LDjo) Eye Contact liquid and vapour irritating Inhalation irritating to respiratory system; headache, dizzyness, drowsiness, intoxication may occur Ingestion may cause headache, dizzyness, drowsiness, intoxication and eventual unconsciousness (Ethyl Acetate, cont'd) EFFECTS OF CHRONIC EXPOSURE General Sensitising Carcinogenic Reproductive Effect Synergistic With Estimated LD50 Estimated LC50 Hands Eyes Respirator Clothing prolonged exposure may cause skin cracking and dermatitis repeated exposure may cause liver and kidney damage may sensitise no none known in humans not known 4100 mg/kg (oral, rat); 20,000 mg/kg (skin, rabbit) 12,500 ppm (inhalation) PROTECTIVE EQUIPMENT "Barricade", "Responder", or "Trellchem" gloves safety glasses with side shields not required if ventilation is adequate (see TWAEV, (I) above) impervious (hands, above) apron , boots, long sleeves, if splasliing is anticipated ENVIRONMENT Leak Precaution Handling Spill inert Waste Disposal 7. dyke to control spillage and prevent environmental contamination ' Fire potentiaL Blanket spill with foam as a precaution against ignition, - ventilate contaminated area; recover free liquid with explosion-proof pumps; absorb residue on an sorbent (dry sand, earth) and store in closed containers for disposal do not flush to sewer; may be incinerated in approved facility STORAGE & HANDLING Store and use in a cool dry envirormient, away from sources of ignition, heat and oxidising agents. Use with adequate ventilation. The product is very flammable and precautions must be taken to reduce the possibility of static discharge which may cause ignition. Ground the container before handling and use non-sparking tools. Do not cut, drill, weld or grind on or near this container. Avoid prolonged contact with skin and wash work clothes frequently. An eye bath and safety shower should be available near the workplace. 8. FIRST AID SKTN: Wash with soap and plenty of water. Remove contaminated clothing and do not reuse until thoroughly cleaned or laundered. EYES: Wash eyes with plenty of water, holding eyelids open. Seek medical assistance promptly if there is any irritation. INHALATION: Remove from contaminated area promptly. CAUTION: Rescuer mast not endanger himself! If breathing stops, administer artificial respiration and seek medical aid promptly. INGESTION: Give plenty of water to dilute product. Do not induce vomiting (sec NOTE below). Keep victim quiet. If vomiting occurs, keep victim's head below the hips to prevent inhalation of vomited material. Seek medical help promptly. NOTE: Inadvertent inhalation of volited material may seriously damage the lungs. The risk and danger of this is greater than the risk of poisoning through absorption of this product. The stomach should be emptied under medical supervision, after the installation of an airway to protect the lungs. Emergency telephone numbers weekdays from 8:00-5:00 at all other times (705) 436-5580 (800) 567-7455 (Philip Environmental) Prepared for Comet Chemical Co. Ltd., by Nicholas Morgan, October 2002 The information herein is given in good faith but no warranty, expressed or implied, is made. PLEASE ENSURE THA T THIS MSDS IS GIVEN TO AND EXPLAINED TO THE PERSON USING THIS PRODUCT. File e-acetat • NPGD0260 - NIOSH Pocket Guide to Chemical Hazards I CDC/NIOSH Page 1 of 1 NIOSH Pocket Guide to Chemical Hazards Ethyl acetate CH3C00C2H5 Synonyms & Trade Names Acetic ester, Acetic ether, Ethyl ester of acetic acid, Ethyl ethanoate Exposure Limits CAS 141-78-6 RTECS AH5425000 OOT ID & Guide 1173 129 NIOSH REL: TWA 400 ppm (1400 mg/m^) OSHA PEL: TWA 400 ppm (1400 mg/m^) IDLH 2000 ppm [10%LEL] See: 141786 Conversion 1 ppm = 3.60 mg/m^ Physical Description Colorless liquid with an ether-like, fruity odor. MW:88.1 BP:17rF VP: 73 mmHg FI.P: 24T IP: 10.01 eV UEL: 11.5% FRZ:-117°F J Sol(77''F): 10% 1 Sp.Gr: 0.90 LEL: 2.0% | Class IB Flammable Liquid: FI.P. below 73°F and BP at or above 100°F. Incompatibilities & Reactivities Nitrates; strong oxidizers, alkalis & acids Measurement Methods NIOSH 1457; OSHA 7 See: NMAM or OSHA Methods Personal Protection & Sanitation Skin: Prevent skin contact Eyes: Prevent eye contact Wash skin: When contaminated Remove: When wet (flammable) Change: No recommendation First Aid (See procedures) Eye: Irrigate immediately Skin: Water flush promptly Breathing: Respiratory support Swallow: Medical attention immediately Important additional Infomiation about respirator selection Respirator Recommendations NIOSH/OSHA Up to 2000 ppm: (APF = 25) Any supplled-air respirator operated in a continuous-ftow nfKxle^/(APF = 25) Any powered, air-purifying respirator with organic vapor cartridge(s)'-/(APF = 50) Any chemical cartrklge respirator with a full facepiece and organic vapor cartridge(s)/(APF = 50) Any air-purifying, full-facepiece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister/(APF = 50) Any self-contained breathing apparatus wHh a full facepiece/(APF = 50) Any supplied-air respirator with a full facepiece Emergency or planned entry into unknown concentrations or IDLH conditions: (APF = 10,000) Any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode/(APF = 10,000) Any supplied-air respirator that has a full facepiece and Is operated in a pressure-demand or other positive- pressure mode in combination with an auxiliary self-contained positive-pressure breathing apparatus Escape: (APF = 50) An^ air-purifying, full-facepiece respirator (gas mask) with a chin-st^e, front- or back-mounted organic vapor canister/Any appropriate escape-type, self-contained breathing apparatus Exposure Routes inhalation, ingestion, skin and/or eye contact Symptoms Irritation eyes, skin, nose, throat; narcosis; dermatitis Target Organs Eyes, skin, respiratory system See also: INTRODUCTION See ICSC CARD: 0367 | NIOSH Home | NIOSH Search | Site Index | Topic List | Contact Us http://www.cdc.gov/niosh/npg/npgd0260.html 5/16/2005 1/20/05 .ORN I [ Material Safety Data Sheets 1 Division of Facilities Services DOD Hazardous Material Informatioii (ANSI Format) For Cornell University Convenience Only NITROGEN Section 1 - Product and Companv Identitication Section 2 - Compositon/Intonnation on Ingredients Section 3 - Hazards Identitication Includine Emergency Overview Section 4 - First Aid Measures Section 5 - Fire Fighting Measures Section 6 - Accidental Release Measures Section 7 - Handling and Storage Section 8 - Exposure Controls & Personal Protection Section 9 - Physical & Chemical Properties Section 10 - Stabilitv & Rcactivitv Data Section 11 - Toxicolouical Infonnation Section 12 - Ecoloaical Intonnation Section 13 - Disposal Considerations Section 14 - MSDS Transport Infonnation Section 15 - RegulatoiA- Information Section 16 - Other Infonnation he information in this document is compiled from information maintained by the United States Department of Defense ^)OD). Anyone using this information is solely reponsible for the accuracy and applicability ofthis informatton to a particular use or situation, "omell University does not in any way warrant or imply the applicability, viability or use ofthis information to any jrson or for use in any situation. Section 1 - Product and Company Identification NITROGEN **Toduct Identincation: NITROGEN ate ofMSDS: 04/01/1984 Technical Review Date: 09/07/1989 FSC: 6830 NIIN: 00-244-2741 '^ibmitter: D DG atus Code: C WFN: 01 * rticle: N it Part: N Manufacturer's Information Vtanufacturer's Name: BIG THREE INDUSTRIES, INC "ist Office Box: 3047 anufacturer's Addressl: 3535 W 12TH ST Manufacturer's Addressl: HOUSTON, TX 77253 1/20/05 Manufacturer's Country: US <<Jeneral Information Telephone: Emergency Telephone: 713-868-0202 '.mergency Telephone: 713-868-0202 ^ISDS Preparer's Name: N/P Proprietary: N Reviewed: Y -.rublished: Y CAGE: 17688 pecial Project Code: N ^em Name: NITROGEN,TECHNICAL Item Manager: pecification Number: NK ^ype/Grade/Class: NK Unit of Issue: nit of Issue Quantity: ^ype of Contamer: CYLINDER Item Description Contractor Information Contractor's Name: AIR LIQUIDE AMERICA CORPORATION ontractor's Addressl: 2700 POST OAK DRIVE contractor's AddressZ: HOUSTON, TX 77056-8229 Contractor's Telephone: 713-896-2896;800-231 -1366 ontractor's CAGE: 17688 Section 2 - Compositon/Information on Ingredients NITROGEN Ingredient Name: NITROGEN ' Igredient CAS Number: 7727-37-9 Ingredient CAS Code: M TECS Number: QW9700000 RTECS Code: M =WT: =WT Code: Volume: =Volume Code: SVT: >WT Code: >Volume: >Volume Code: WT: <WT Code: _Volume: <Volume Code: % Low WT: % Low WT Code: "'• High WT: % High WT Code: ) Low Volume: % Low Volume Code: % High Volume: % High Volume Code: •'.Text: 100 I Enviromental Weight: Other REC Limits: N/R '^SHA PEL: NOT ESTABLISHED OSHA PEL Code: M SHA STEL: OSHA STEL Code: ACGIH TLV: ASPHYXIANT; 9192 ACGIH TLV Code: M * CGIH STEL: N/P ACGIH STEL Code: PA Reporting Quantity: DOT Reporting Quantity: tp://msds.ehs.comell.edu/msds/msdsdod/a28/ml 3612.htm 1/20/05 •zone Depleting Chemical: N Section 3 - Hazards Identification, Including Emergency Overview NITROGEN :ealth Hazards Acute & Chronic: NRTROGEN IS NONTOXIC, BUT MAY PRODUCE SUFFOCATION BY _1SPLACING THE OXYGEN IN THE AIR. EXPOSURE TO OXYGEN-DEFICIENT ATMOSPHERES MAY CAUSE DIZZINESS, NAUSEA, VOMITING, DIMINISHED MENTAL ALERTNESS, LOSS OF CINSCIOUSNESS & ~ EATH. Signs & Symptoms of Overexposure: "EE "HEALTH HAZARDS" Medical Conditions Aggravated by Exposure: ^'/R LD50 LCSO Mixture: N/R _oute of Entry Indicators: Inhalation: YES Skin: NO _ Ingestion: NO ^arcenogenicity Indicators NTP: N/P lARC: N/P OSHA: N/P Carcinogenicity Explanation: N/R Section 4 - First Aid Measures NITROGEN irst Aid: PERSONS SUFFERING FROM LACK OF OXYGEN SHOULD BE MOVED INTO FRESH AIR. ASSISTED RESPIRATION & SUPPLEMENTAL OXYGEN SHOULD BE GIVEN IF THE VICTIM IS NOT BREATHING. ELF-CONTAINED BREATHING APPARATUS MAY BE REQUIRED TO PREVENT ASPHYXIANTION OFRESCUE WORKERS. Section 5 - Fire Fighting Measures NITROGEN ire Fighting Procedures: ^RE FIGHTERS SHOULD WEAR SELF-CONTAINED BREATHING APPARATUS. Unusual Fire or Explosion Hazard: ITROGEN WILL ACT AS A SIMPLE ASPHYXIANT IF IT DISPLACES OXYGEN, ^extinguishing Media: USE MEDIA SUITABLE FOR SURROUNDING FIRE. lash Point: Flash Point Text: N/R Autoignition Temperature: Autoignition Temperature Text: N/A - Lower Limit(s): N/R Upper Limit(s): N/R tp://msds.ehs.comell.edu/msds/msdsdod/a28/ml 3612.htm 1/20/05 Section 6 - Accidental Release Measures NITROGEN pill Release Procedures: SHUT OFF NITROGEN SOURCE IF POSSIBLE. VENTILATE ENCLOSED AREAS TO PREVENT FORMATION '^F OXYGEN-DEFICIENT ATMOSPHERES. Section 7 - Handling and Storage NITROGEN Handling and Storage Precautions: ither Precautions: Section 8 - Exposure Controls & Personal Protection NITROGEN epiratory Protection: ^SE SELF-CONTAINED BREATHING APPARATUS IN OXYGEN-DEFICIENT ATMOSPHERES. RESPIRATORS WILL NOT FUNCTION. entilation: ^ENTS SUFFICIENT TO AVOID HIGH CONCENTRATIONS OF NITROGEN. Protective Gloves: ONE _ye Protection: NONE Other Protective Equipment: NONE STATED ^ork Hygenic Practices: N/P „ipplemental Health & Safety Information: NITROGEN IS NON-TOXIC BUT CAN ACT AS AN ASPHYXIANT BY DISPLACING THE NECESSARY AMOUNT OF AIR TO SUSTAIN LIFE. Section 9 - Physical & Chemical Properties NITROGEN CC: G3 NRC/State License Number: *'et Property Weight for Ammo: oiling Point: Boiling Point Text: -320.4F Melting/Freezing Point: Melting/Freezing Text: N/K 'decomposition Point: Decomposition Text: N/K apor Pressure: GAS Vapor Density: .0724 LBCF Fercent Volatile Organic Content: P->eciric Gravity: 0.967 AT 70F olatile Organic Content Pounds per Gallon: pH:7 *'olatile Organic Content Grams per Liter: iscosity: N/P Evaporation Weight and Reference: N/K «=olubility in Water: 2.33 VOL % ppearance and Odor: COLORLESS, ODORLESS, TASTELESS GAS Fercent Volatiles by Volume: 100 '^orrosion Rate: N/K Section 10 - Stability & Reactivity Data tp://msds.ehs.comell.edu/msds/msdsdod/a28/m 13612.htm 1/20/05 NITROGEN Stability Indicator: YES iaterials to Avoid: JfR Stability Condition to Avoid: lONE STATED lazardous Decomposition Products: N/R "lazardous Polymerization Indicator: NO 'onditions to Avoid Polymerization: N/R " Section 11-Toxicological Information NITROGEN oxicological Information: N/P ~ Section 12 - Ecological Information NITROGEN cological Information: n./P Section 13 - Disposal Considerations NITROGEN /aste Disposal Methods: _ECURE CYLINDER & BLOW DOWN SLOWLY TO THE ATMOSPHERE IN A WELL-VENTILATED AREA OR OUTDOORS. Section 14 - MSDS Transport Information NITROGEN ransport Information: N/P Section 15 - Regulatory Information NITROGEN : VRA Title III Information: iv/P Federal Regulatory Information: 'P Mate Regulatory Information: N/P Section 16 - Other Information NITROGEN ^her Information: N/P »-oduct Identification: NITROGEN Transporation ID Number: 60280 HMIS Transportation Information tp://msds.ehs.comell.edu/msds/msdsdod/a28/m 13612.htm 1/20/05 responsible Party CAGE: 17688 _)ate MSDS Prepared: 04/01/1984 Date MSDS Reviewed: 07/20/1989 IFN: 07/20/1989 _ ubmitter: D DG Status Code: C Container Information Unit of Issue: Container Quantity: Type of Container: CYLINDER Net Unit Weight: __rticle without MSDS: N Technical Entry NOS Shipping Number: adioactivity: _orm: Net Explosive Weight: oast Guard Ammunition Code: _ lagnetism: N/P AF MMAC Code: ~ OD Exemption Number: imited Quantity Indicator: Multiple Kit Number: 0 ' 'it Indicator: N it Part Indicator: N Review Indicator: Y ' dditional Data: Department of Transportation Information OT Proper Shipping Name: NITROGEN, COMPRESSED DOT PSN Code: KLZ 'Symbols: OT PSN Modifier: Hazard Class: 2.2 '^N ID Number: UN 1066 OT Packaging Group: Label: NONFLAMMABLE GAS ^•jecial Provision(s): ickaging Exception: 306 Non Bulk Packaging: 302 "ulk Packagmg: 314,315 [aximimum Quanity in Passenger Area: 75 KG Maximimum Quanity in Cargo Area: 150 KG *^*:ow in Vessel Requirements: A equirements Water/Sp/Other: IMO Detail Information »MO Proper Shipping Name: NITROGEN, COMPRESSED /IO PSN Code: KSR IMO PSN Modifier: IMDG Page Number: 2163 N Number: 1066 CN Hazard Class: 2(2.2) tp://msds.ehs.comell.edu/msds/msdsdod/a28/m 13612.htm 1/20/05 MO Packaging Group: - subsidiary Risk Label: - EMS Number: 2-04 ledical First Aid Guide Number: NON lATA Detail Information lATA Proper Shipping Name: NITROGEN, COMPRESSED \TA PSN Code: SBP -_\TA PSN Modifier: lATA UN Id Number: 1066 \TA UN Class: 2.2 _ ubsidiary Risk Class: UN Packaging Group: \TA Label: NON-FLAMMABLE GAS _ackaging Note for Passengers: 200 Maximum Quantity for Passengers: 75KG ackaging Note for Cargo: 200 _Iaximum Quantity for Cargo: 150KG Exceptions: AFI Detail Information _FI Proper Shipping Name: NITROGEN, COMPRESSED AFI Symbols: FI PSN Code: SBP FI PSN Modifier: AFI UN Id Number: UN 1066 * FI Hazard Class: 2.2 FI Packing Group: N/A AFI Label: •Special Provisions: P5 ack Pack Reference: A6.3, A6.6 HAZCOM Label Information "roduct Identification: NITROGEN AGE: 17688 Assigned Individual: N '"ompany Name: AIR LIQUIDE AMERICA CORPORATION ompany PO Box: Company Street Addressl: 2700 POST OAK DRIVE '"ompany Street Address2: HOUSTON, TX 77056-8229 US ealth Emergency Telephone: 713-868-0202 Label Required Indicator: Y '^ate Label Reviewed: 12/16/1998 :atus Code: C Manufacturer's Label Number: i^ate of Label: 12/16/1998 ear Procured: N/K Organization Code: F '"hronic Hazard Indicator: N/P ye Protection Indicator: N/P Skin Protection Indicator: N/P Respiratory Protection Indicator: N/P gnal Word: N/P Health Hazard: Contact Hazard: ire Hazard: Reactivity Hazard: .1p://msds.ehs.comell.edu/msds/msdsdod/a28/ml 3612.htm 1. CHEMICAL PRODUCT AND COMPANY IDENTIFICATION Identification Product Name: SODIUM TRIMETAPHOSPHATE ANHYDROUS Reference Number AST10055 Date: 28 September 2004 Use of the substance or preparation Water treatment, Mold Release Agent, Food Ingredient, Cleaning Ingredient Company/Undertaking Identification Worldwide Hqts Europe Hqts ASTARIS LLC ASTARIS S.r.l. 622 Emerson Road - Suite 500 Via Brescia 26 St. Louis, Missouri 63141 20063 Cernusco sul Naviglio Ml Italy Emergency telephone In Europe call +32 (0) 3 568 5123 In USA call CHEMTREC: 1 800 424 9300 In Canada call CANUTEC: 1 613 996 6666 General Infonmation: +32 (0) 2 921 02442 (Europe) +1 800 244 6166 (Worldwide) 2. COMPOSITION/INFORMATION ON INGREDIENTS Composition Substance CAS No. Sodium Trimetaphosphate Anhydrous 7785-84-4 3. HAZARDS IDENTIFICATION Classification of the substance/orenaration EC Classification None Safety Phrase None Human Health Effects %w/w EINECSNo. 232-088-3 Risk Phrase None Likely Routes of Exposure: Skin contact and inhalation EYE CONTACT: No more than slightly irritating based on toxicity studies. The dry powder may cause foreign body irritation in some individuals. Astaris Material Safety Data Sheet Material:Sodium Trimetaphosphate Anhydrous Page 2 of 6 Reference No.: AST10055 September 28. 2004 SKIN CONTACT: No more than or slightly irritating based on toxicity studies. Prolonged contact with the dry powder may cause drying or chapping ofthe skin. INHALATION: lnhalatk)n of the dust may cause coughing and sneezing. INGESTION: Not toxic if swallowed based on toxicity studies. No significant adverse health effects are expected if only small amounts (less than a mouthful) are swallowed. Refer to Section 11 for toxicological information. Environmental Effects This material is not expected to product any significant adverse environmental effects when recommended use instructions are followed. 4. FIRST AID MEASURES General Treatment is symptomatic and supportive. Eve contact Immediate first aid is not likely to be required. However, this material can be removed with water. Remove material from eyes, skin and clothing. Wash heavily contaminated clothing before reuse. Skin contact Immediate first aid is not likely to be required. However, this material can be removed with water. Remove material from eyes, skin and clothing. Wash heavily contaminated clothing before reuse. Inhalation Immediate first aid is not likely to be required. However, if symptoms occur, remove to fresh air. Ingestion Immediate first aid is not likely to be required. A physician or Poison Control Center can be contacted for advice. 5. FIRE FIGHTING MEASURES Extinguishing media Non-combustible No special requirement. To extinguish fire use water spray, dry chemical, carbon dioxide, or appropriate foam Unsuitable extinguishable media Non-combustible No special requirement. Exposure hazards No special considerations. Protective eguipment As a general precaution, firefighters and others exposed, wear self-contained breathing Astaris Material Safety Data Sheet Material:Sodium Trimetaphosphate Anhydrous Page 3 of 6 Reference No.: AST10055 September 28. 2004 apparatus. 6. ACCIDENTAL RELEASE MEASURES Personal precautions Avoid unnecessary exposure and remove all material from eyes, skin and clothing. Environmental precautions Small quantities: See below Large quantities: See below Method for cleaning up In case of spill, sweep, scoop or vacuum and remove. Flush residual spill area with water. 7. HANDLING AND STORAGE Handling: Handle in accordance with good industrial hygiene and safety practices. These practices include avoiding unnecessary exposure and removal of material from eyes, skin, and clothing. Engineering measures Provide natural or mechanical ventilation to minimize exposure. The use of local mechanical exhaust ventilation is preferred at sources of air contamination such as open process equipment. Consult National Fire Protection Association (NFPA) Standard 91 for design of exhaust systems. Storage Store in cool, dry place to maintain product performance. Product is very hygroscopic and should be stored in a dry area in poly or vapor barrier bags to prevent moisture pk:kup and caking. 8. EXPOSURE CONTROLS/PERSONAL PROTECTION Occupational Exposure limit ACGIH TLV 10 mg/m3 (inhalable) 8-hr TWA, 3 mg/m3 (respirable) 8-hr TWA OSHA PEL 15 mg/m3 (tolal dust) 8-hr TWA, 5 mg/m3 (respirable) 8-hr TWA OSHA and ACGIH have not established specific exposure limits for this material. However, OSHA and ACGIH have established limits for particulates not otherwise regulated (PNOR) and particulates not othenvise classified (PNOC) which are the least stringent exposure limits applicable to dusts. Components referred to herein may be regulated by specific Canadian provincial legislation. Please refer to exposure limits legislated for the province in which the substance will be used Respiratory protection Avoid breathing dust. Use NIOSH/MSHA approved respiratory protection equipment when airborne exposure limits are exceeded. Consult the respirator manufacturer to determine appropriate type equipment for a given application. Observe respirator use limitations specified by NIOSH/MSHA or the manufacturer. Respiratory protection programs must comply with 29 C.F.R. 1910.134 and or European Standard EN149. Hand/Skin protection Although this product does not present a significant skin concern, minimize skin contamination by following good industrial practice. Wearing protective gloves is recommended. Wash hands and Astaris Material Safety Data Sheet MateriaLSodium Trimetaphosphate Anhydrous Page 4 of 6 Reference No.: AST10055 September 28. 2004 contaminated skin thoroughly after handling. Eye protection This product does not cause significant eye irritation or eye toxicity requiring special protection. Use good industrial practice to avoid eye contact. 9. PHYSICAL AND CHEMICAL PROPERTIES General Infonnation Chemical Formula: Na3(P03)3 Form: Fine, crystalline powder Color: White Odor: Odoriess Important health, safetv and environmental information pH: 6.0 - 8.0 (as a 1% solution @ 25 degrees C) Melting Point: Begins to melt incongruently at 420 degrees C; completely melted 625 degrees C Bulk Density: 64 - 70 (Ibs./cu. ft.) Solubility in Water: 20 (g/1 OOg H20) @ 25 degrees C NOTE: These physical data are typical values based on material tested but may vary from sample to sample. Typical values should not be construed as a guaranteed analysis of any specific lot or as specifications for the product. 10. STABILITY AND REACTIVITY Product is stable under normal conditions of storage and handling. Conditions to avoid None known. Materials to avoid None known. Hazardous decomposition None known. 11. TOXICOLOGICAL INFORMATION Laboratory data The dry powder may cause foreign body irritation in some individuals. Prolonged contact with the dry powder may cause drying or chapping of the skin. Excessive inhalatton of dust may be annoying and can mechanically impede respiration. Data from Astaris single-dose (acute) animal studies with this material are given below: Oral - rat LD50: > 10,600 mg/kg; practically nontoxic Eye Irritation - rabbit: 8.3/110.0; slightly irritating Skin Irritation - rabbit (24-hr exp): 0.0/8.0; practically nonirritating Rats fed this material in their diet for one month showed decreased growth, increased kidney-to- body weights and slight kidney changes. Rats fed this material for two years also showed decreased weight gain, as well as blood changes and increased mortality. No increase in tumors was reported. No adverse effects in reproductive capacity were reported in a multigeneration Astaris Material Safety Data Sheet Material:Sodium Trimetaphosphate Anhydrous Page 5 of 6 Reference No.: AST10055 September 28. 2004 study using rats fed this material. 12. ECOLOGICAL INFORMATION Environmental toxicitv Astaris has not conducted environmental toxicity studies with this product. Environmental fate Astaris has not conducted biodegradation studies with this product since when dissolved / hydrolyzed in water it yields completely mineralized materials. 13. DISPOSAL CONSIDERATIONS European waste catalog number Unknown Disposal Considerations This material when discarded is not a hazardous waste as that tenn is defined by the Resource, Conservation and Recovery Act (RCRA), 40 CFR 261. Dry material may l>e landfilled or recycled in accordance with local, state and federal regulations. Consult your attorney or appropriate regulatory officials for information on such disposal. 14. TRANSPORT INFORMATION The data provided in this section is for information only. Please apply the appropriate regulations to properly classify your shipment for transportation. Road/Rail. Sea and Air IMDG/UN Not regulated. ICAO/IATA Not regulated. RID/ADR Not regulated. Canadian TDG Not regulated. US DOT Not regulated. 15. REGULATORY INFORMATION EC Label Hazard symbol: none Chemical Inventory USA TSCA; Listed Canada DSL: Listed EC: Listed Other information WHMIS Classification: Not controlled. SARA Hazard Notification Hazard Categories Under Title III Rules (40 CFR 370): Not applicable Section 302 Extremely Hazardous Substances: Not applk:able Section 313 Toxic Chemical(s): Not applk:able CERCLA Reportable Quantity: Not applicable Astaris Material Safety Data Sheet Material:Sodium Trimetaphosphate Anhydrous Reference No.: AST10055 Page 6 of 6 September 28. 2004 This product has been classified in accordance with the hazard criteria of the Canadian Controlled Products Regulation and the MSDS contain all the infomiation required by the Canadian Controlled Products Regulation. 16. OTHER INFORMATION Suggested NFPA Rafing Suggested HMIS Rating Reason for revision: Corrected pH & solubility data. 2003 Drafted in accordance with ECC Dir 2001/58/EC Health 1 1 Fire 0 0 Reactivity 0 0 Addittonal Infomiation E E = safety glasses, gloves, dust respirator Supersedes MSDS dated: March 24, Nutrifos® is a registered trademari( of Astaris LLC Astaris® is a trademark of Astaris LLC Although the information and recommendations set forth herein (hereinafter "Information") are presented in good faith and believed to be conrect as of the date hereof, Astaris LLC makes no representations as to the completeness or accuracy thereof Infomnatkxi is supplied upon the condition that the persons receiving same will make their own determination as to its suitability for their purposes prior to use. In no event will Astaris LLC be responsible fbr damages of any nature whatsoever resulting from the use of or reliance upon information. NO REPRESENTATIONS OR WARRANTIES, EITHER EXPRESS OR IMPUED. OF MERCHANTABILITY, FITNESS FOR A PARTICULAR PURPOSE OR OF ANY OTHER NATURE ARE MADE HEREUNDER WITH RESPECT TO INFORMATION OR THE PRODUCT TO WHICH INFORMATION REFERS AST10055.1100.doc SLAS J/H ^^ Quality ProdiK riTVRIS PRODUCT DATA SHEET Quality Products. Exceptional Respont*. PRODUCT: Sodium Trimetaphosphate, Anhydrous (STMP) NSF GRADE: Technical CODE: 000 GENERAL DESCRIPTION: Anhydrous white powder FORMULA: (NaP03)3 MOLECULAR WEIGHT: 305.94 CAS NO.: 7785-84-4 DATE EFFECTIVE: Januarv 1. 2004 CHARACTERISTICS SPECIFICATION LIMITS Assay, % NasPsOg 95.0 Minimum Loss on Ignition, % 0.5 Maximum Sizing, USSS: Retained on 100 Mesh, % 10 Maximum NOTE: Specification Limits are subject to change from time to time. Please contact us for current data sheet. Production Location: Carteret, NJ Packaging: 50 Ib. multiwall bags; super sacks Labeling Requirements: Product label Shipping Classification: Sodium Phosphate Handling Precautions: No precautionary statement required on label. Handle in accordance with good industrial hygiene and safety practices. These include avoiding unnecessary exposure and removal of material from eyes, skin, and clothing. This Product Data Sheet is subject to the terms and conditions on the reverse side hereof. SODIUM TRIMETAPHOSPHATE, ANHYDROUS (STMP) TECHNICAL POWDER Sodium trimetaphosphate (STMP) is a salt of a strong base and a strong acid. Chemically, it has no buffering or sequestering power and, hence, no inherent detergent building properties. However, when reacted with caustic soda, STMP converts rapidly and completely to sodium tripolyphosphate (STP), which is probably the most efficient builder known on a cost/performance basis. When caustic potash is used in place of caustic soda a mixed sodium/potassium salt of tripolyphosphate with enhanced solubility characteristics is formed. By controlling the conversion conditions, STMP can be used as the source of phosphate in a conventional spray- drying detergent process. If no spray tower is available, the Astaris LLC, "Batch Fluff Process" can be used for producing a porous, granular product directly from a detergent slurry based on STMP, thus eliminating the spray tower operation completely. Key Properties: • Low density, high quality granular detergents can be produced without spray drying. • Both anionic and mixed active detergents with a range of 30-60% STP are possible. • Product density can be controlled over a range by control of process variables. • Granulated intermediates can be blended with chlorinated isocyanurates chlorinating compositions to produce dry bleaches or automatic dishwashing compounds. • A mixed sodium/potassium tripolyphosphate (SKTP) salt can be prepared that possesses enhanced solubility over regular sodium tripolyphosphate. • Shelf-life = 18 months Applications; • Consumer and industrial detergents and cleaning products, particularly liquid products which exhibit enhanced tripolyphosphate solubility. • Dry bleach bases. • Phosphate detergent intermediate. • Potable Water Treatment: Astaris sodium trimetaphosphate confonns to the requirements of ANSI / NSF Standard 60. Used for corrosion & scale conlrol. Maximum Use Level = 11 mg/L. • STMP can be used in preparation of granular detergent compounds utilizing the "Batch Fluff Process." FOR MORE COMPLETE INFORMATION ON PROPERTIES AND SAFE HANDLING OF THIS MATERIAL, SEE THE ASTARIS MATERIAL SAFETY DATA SHEET (MSDS). NOTICE: Although the infonnation and recommendations set forth herein (hereinafter "Information") are presented in good faith and believed to be correct as ofthe date hereof, Astaris LLC makes no representations or warranties as to the completeness or accuracy thereof. Information is supplied upon the condition that the persons receiving same will make their own determination as to its suitability for their purposes prior to use. In no event will Astaris LLC be responsible for damages ofany nature whatsoever resulting ffom the use ofor reliance upon Information or the product to which Information refers. Nothing contained herein is to be construed as a recommendation to use any product, process, equipment or formulation in conflict with any patent, and Astaris LLC makes no representation or warranty, express or implied, that the use thereof will not infringe any patent. The data set forth herein are based on samples tested and are not guaranteed for all samples or applications. Such dala are intended as guides and do not reflect product specifications for any particular product NO REPRESENTATIONS OR WARRANTIES, EITHER EXPRESS OR IMPLIED, OR MERCHANTABILITY, FITNESS FOR A PARTICULAR PURPOSE OR OF ANY OTHER NATURE ARE MADE HEREUNDER WITH RESPECT TO INFORMATION OR THE PRODUCT TO WHICH INFORMATION REFERS. ASTARIS LLC © January, 2004 Corporate Offices: 622 Emerson Road Suite 500 St. Louis, Missouri 63141 314-983-7500 For order assistance, please call our Customer Service Department Toll Free: 1-800-244-6169 KLEINFELDER APPENDIX C Abbreviated Sampling and Analysis Plan Pilot Test for Well B-6 Promontory Facility Promontory, Utah Kl KtEINFELDER INTRODUCTION 1.1 PROJECT BACKGROUND ATK is a facility that manufactures rocket motors and fuel amongst other items. As a result of years of processing, waste handling practices have resulted in chemical releases to groundwater. Beneath a portion of the ATK Promontory facility, the groundwater has become impacted with perchlorate. The pilot test will explore the viability of in situ perchlorate remediation using vapor amendment and sparging. 1.2 SCOPE AND PURPOSE The purpose of the pilot test is to assess if ethyl acetate and nitrogen, when introduced into the groundwater by sparging, are a suitable vapor amendment (or electron donor) for degrading perchlorate in situ at the Site. The scope of the pilot test involves drilling a sparge well approximately 25 feet upgradient of an existing monitoring well, well B-6, to approximately 130 feet bgs. The vapor amendment will be supplied by a simple system where ethyl acetate is mixed with nitrogen and applied at a desired rate firom pressure in the supply tank. Groundwater samples will be taken before, during, and after the pilot test amendment injection period to evaluate the effectiveness ofthe application for degrading perchlorate. .1.3 LOCATION As described in the work plan, well B-6 has been chosen as the monitoring well that will be the down gradient observation point for the sparge well. The concentrations of perchlorate are relatively high and the well is screened in desirable alluvial deposits with an adequate aquifer thickness. Results from groundwater samples taken on April 7, 2005 have been attached to this appendix for reference. ATK/51278.001/SLC5R031 Page C-l June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 1.4 PROJECT ORGANIZATION AND RESPONSIBILITIES This project is under the direction of the management at ATK. Oversight and pilot system setup will be performed by Kleinfelder. Mike Zimmerman Well Service will perform sparge well installation. ATK will provide groundwater sampling services. ATK/51278.001/SLC5R031 Page C-2 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 2. GROUNDWATER SAMPLING 2.1 SAMPLING PROCEDURE Well B-6 and possibly well T-l at the ATK - Promontory Facility will be sampled using low- flow procedures. ATK will perform the groundwater sampling. Groundwater will be purged from the monitoring well to remove stagnant and stratified groimdwater from the well casing and so that the collected sample is representative ofthe surrounding aquifer. 2.1.1 Field Measurements As the monitoring well is purged, field measurements will be monitored for groundwater quality changes. Samples will not be collected until the field measurement parameters have stabilized. Instruments will be calibrated to the manufacturer's instructions before taking field measurements and recorded on the field log. Samples of discharging groundwater shall be monitored through a flow cell for field measurements of pH, conductivity, TDS, temperature, ORP, and DO. Measurements shall be recorded on sampling log form. The well shall be purged until field measurements stabilized ±10%. 2.1.2 Low-Flow Purging During the pilot test, the top ofthe casing of well B-6 will be sealed to minimize the intrusion of air into the casing. The well will be purged using low-flow techniques so as not to disturb the anaerobic conditions surrounding aquifer. ATK will use a low-flow controller to operate the pump and will purge at a rate approximately between 100 and 5(X) milliliters per minute until field parameters stabilize ±10% and total drawdown on the initial groundwater level is not greater than 0.33 feet (0.1 meter). ATKy51278.001/SLC5R031 Page C-3 June 22,2005 Copyright 2005 Kleinfelder, Inc. Kl KLEINFELDER 2.1.3 Sample Collection After the well has been purged and the field measurements have stabilized, the groundwater shall be sampled. Sample collection will be conducted using a stabilized flow from the pump during low-flow purging. New disposable gloves shall be donned before taking the sample to avoid potential cross-contamination with the purge water. Although not required for each sampling event in this program, groundwater will be sampled first for volatile organic compounds (VOCs) when required. The volatile organic analysis (VOA) vials shall be gently filled from the bottom up and capped without any headspace or bubbles. Next the sample bottle for the perchlorate analysis shall be taken. The remaining sample bottles for inorganic, metals, and explosive analyses can be filled in any order. 2.1.4 Sample Frequency and Schedule Two lists of analytes will be sampled from the down gradient well B-6 and possibly T-l. Pre- and post- injection samples will be analyzed for the full list, and ongoing monitoring samples during the pilot test will be analyzed for the partial list. The purpose of the partial list is to monitor critical indicator analytes that will guide changes to the pilot system injection rates and mass loading. A tentative schedule has been provided in Table C-l. Generally the lag between samples will increase over time since more dramatic changes are expected at the startup of the system. 2.1.5 Sample Transport After collection of each szimple, the time of coUection shall be recorded in the field log, on the sample label, and on the chain-of-custody form in indelible ink. The sample bottles will be chilled with ice in coolers to 4±2 degrees Celsius for shipment to the laboratory. The chain-of- custody will accompany the samples and shall be signed by the person in possession. ATK/51278.001/SLC5R031 Page C-4 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 2.2 PRE-INJECTION AND POST-INJECTION SAMPLES Table C-2 lists the constituents and analytical methods for the full suite of analyses. Samples for these analyses will be collected before and after the injection period. (Note: A subset or partial list is shown in Table C-3 for those analyses to be performed on samples during injection monitoring as described in the next section.) Thiokol Laboratory or Chemtech-Ford shall perform the analyses. It is recommended that the samples for perchlorate be passed through a 0.2 micron filter at the laboratory as soon as they are received to remove bacteria that could affect the analyses. A standard tum-around-time will be requested from the laboratories for the fijll analytical list. 2.3 fNJECTlON PERIOD SAMPLES To monitor changes in perchlorate concentrations during the pilot test injection, groundwater samples will be collected from well B-6 and possibly from well T-l. Well T-l may be monitored as a cross or down gradient well. An expedited tum-around time of 24 hours will be requested whenever possible from the analytical laboratory on for the partial analytical list including analyses for perchlorate, nitrate, phosphate, phosphorus, and pH/ORP (Table C-3). This will allow for rapid response to optimize the remediation system flow rates and vapor amendment concentrations. 2.4 FIELD PARAMETER MEASUREMENTS A down-hole logging probe as rented by Kleinfelder will be deployed in well B-6 for continuous monitoring of pH, temperature, DO, conductivity, and OPR. If ORP values exceed those necessary to remediate perchlorate, it is possible that metals could be mobilized in a reducing enviroiunent. Should this condition occur, application rate or concentration of the vapor amendment would be decreased accordingly. The reducing environment should respond quickly with metals precipitating immediately down gradient ofthe pilot test area. ATKy51278.001/SLC5R031 Page C-5 June 22,2005 Copyright 2005 Kleinfelder, Inc. KLEINFELDER 2.5 QUALITY CONTROI7QUALITY ASSURANCE Duplicate and matrix spike/matrix spike duplicate samples shall be taken for approximately ten percent of the overall number of samples for reproducibility of the laboratory instmments. The analytical data will be reviewed for quality control and data completeness. ATK/51278.001/SLC5R031 Page C-6 June 22,2005 Copyright 2005 Kleinfelder, Inc. Table C-l Pre-injection, Post-Injection, and Final Monitoring Events Schedule for Groundwater Sample CoUection Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility Sample | Date^^^^MBEwrimate Lag Full List Pre-injection Pre-System Adjustment (if needed) Post-Inj ection 7/22/05 8/24/05 9/23/05 NA 32 30 Partial List GW Sampling I GW Sampling 2 GW Sampling 3 GW Sampling 4 GW Sampling 5 (optional) GW Sampling 6 (optional) GW Sampling 7 (optional) 7/26/05 8/1/05 8/5/05 8/15/05 8/29/05 9/5/05 9/13/05 3 4 5 10 5 7 8 Note: GW-groundwter Time between and number of samples will ultimately depend on field conditions. Dates and lag times have been adjusted so sampling will occur on working days. ATK/51278.001/SLC5R03I Copyright 2005 Kleinfelder, Inc. Page 1 of 1 June 22, 2005 Table C-2 Pre-injection, Post-Injection, and Final Monitoring Events Ftdl Analytical List for Groundwater Samples Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory FaciUty Analyte Chlonde Nitrite-N Bromide Nitrate-N Sulfate Chlorate Sulfide Chemical Oxygen Demand Ammonia-N Phenol Alkalinity Fluoride Phosphate Phosphorus I otal Dissolved Solids Total Suspended Solids Aluminum (dissolved) Arsenic (dissolved) Barium (dissolved) Cadmium (dissolved) Calcium (dissolved) Chromium (dissolved) Iron (dissolved) Lead (dissolved) Magnesium (dissolved) Mercury (dissolved) Potassium (dissolved) Selenium (dissolved) Silver (dissolved) Sodium (dissolved) Zinc (dissolved) Aluminum Arsenic Barium Cadmium Calcium Chromium Iron Lead Magnesium Mercury Potassium Selenium Silver Sodium Zinc Perchlorate* Acetone Acrolein Acrylonifrile CASNOT^IHBAM i 7775-09-9 7664-41-7 108-95-2 14265-44-2 7723-14-0 7429-90-5 7440-38-2 7440-39-3 744043-9 7440-70-2 744047-3 7439-89-6 7439-92-1 7439-954 7439-97-6 7440-09-7 778249-2 7440-224 7440-23-5 7440-66-6 7429-90-5 7440-38-2 7440-39-3 744043-9 7440-70-2 744047-3 7439-89-6 7439-92-1 7439.954 7439-97-6 7440-09-7 778249-2 7440-224 7440-23-5 7440-66-6 67-64-1 107-02-8 107-13-1 IC 300.0 Anions IC 300.0 Anions IC 300.0 Anions IC 300.0 Anions IC 3O0.O Anions Chlorate by IC Sulflde 376.1 COD Ammonia-N PhenoUcs 9066 Alkalinity W Fluoride 34(^2 W 300.0 365 TOS 160.1 TCS 160.2 6010B Metals W 6010B Metals"W 6010B Metals'W fiOlOBMetals'W 6010BMetals"W 6010B Metals W 6010B Metals'W 6010B Metals'W 6010B Metals'W 7470A • 6010B Metals W 6010B Metals'W 6010B Metals'W 6010B Metals W 6010B Metals W 6010B Metals'W 6010B Metals'W 6010B Metals'W 6010B Metals W 6010B Metals W 6010B Metals W 6010B Metals W 6010B Metals W 60I6B Metals W 7470A ' 6010B Metals W MIOB Metals'W MIOB Metals'W 6010B Metals'W MIOB Metals'W Perchlorate 3T4 8260B1X W 8260BLX W 8260B IX'W ATK/51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page 1 of 3 June 22, 2005 Table C-2 Pre-injection, Post-Injection, and Final Monitoring Events Full Analytical List for Groundwater Samples Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility Analyte Allyl Chloride [lyl Bi CAS No. 107-05-1 BRTOKV" 71-43-2 8260B1X'W 8260B1X'W enzene Bromobenzene Bromochloromethane 108-86-i 74-97-5 8260B DTW Bromodichloromethane Bromoform 75-27-4 82MB IX'W 8260B IX'W 75-25-2 74-83-9 Bromomethane 1-Butanol 8260B IX'W 71-36-3 8260B IX'W 82«)B1X'W 2-Butanone sec-Butylbenzene' 78-93-3 135-98-8 8260B1X'W tert-Butylbenzene 98-06-6 8260B1X"W 8260BIX^ Carbon Disul tide Carbon letrachloride 75-15-0 56-23-5 8260B IX'W Chlorobenzene Chloroethane 108-90-7 8260B IX'W 8260B IX'W 75-00-3 110-75-8 2-Chloroethylvinyl Ether 8260BIX'W Chloroform Chloromethane 67-66-3 8260B IX'W 8260B IX'W 74-87-3 126-99-8 Chloroprene (2-Chloro-1,3-Butadiene7 2-Chlorotoluene 8260B IX'W 9549-8 8260B IX'W 8260B IX'W 4-Chlorotoluene Cyclohexanone 106-434 108-94-1 8260BIX'W 1,2-Dibromo-3-Chloropropan~ Dibromochlorometnane 96-12-8 8260B1X'W 8260BIX'W 12448-1 106-934 1,2-Dibromoethane~ Dibromomethane 8260B1X'W 74-95-3 8260BIX'>^ 8260B1X'W 1,2-Dichlorobenzeiie" 1,3-Dichlorobenzene 95-50-1 541-73-1 8260BIX'W 1,4-Dichlorobenzene 1,1 -Dichloroethane 10646-7 8260B1X"W 8260B IX'W 75-34-3 107-06-2 1,2-Dichloroethatie" 1,1 -Dichloroethene 82A0B1X W 75-354 8260B IX'W 8260B IX'W cis-1,2-Dichloroethene 156-594 75-71-8 Dichlorodifluoromethane 1,2-Dichloropropane 8260B1X'W 78-87-5 8260B IX'W 8260BIX^ 1,3-DichToropropane 2,2-Dichloropropane" 142-28-9 590-20-7 8260B LXW 1,1 -Dichloropropene" 563-58-6 8260B1X"W 8260BIX'W CIS-1,3-Dichloropropene trans-1,3-Dichloropropene 10061-01-5 10061-02-6 8260B1X"W Ethyl Acetate 141-78-6 8260BIX'W 8260BIX'W Ethylbenzene Ethyl Ether"^ 100-41-4 60-29-7 8260BIX"W Ethyl Methacrylate" 97-63-2 8260B IX'W 8260BIX'W 8260B IX'W 1,1,2-Trichloro-1,2,2- Iritluoroethane Hexachlorobutadiene 76-13-1 87-68-3 2-Hexanone 591-78-6 8260BIX'W 8260B IX'W Isopropyl Alcohol Isopropylbenzene 67-63-0 98-82-8 8260B IX'W m 4-Methyl-2-Pentanone 108-10-1 82601i IX W ATK/51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page 2 of 3 June 22, 2005 Table C-2 Pre-Injection, Post-Injection, and Final Monitoring Events Full Analytical List for Groundwater Samples Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility Analyte 2-Methyl-1 -Propanor(Isobutyl AlcoholJ 2-Nitropropane CAS No. 78-83-1 7946-9 82WJB IX'W itropropa 99-87-6 126-98-7 8260B IX'W 8260BIX'W l-Isopropyltolue Methacrylonitril luene Methyl Iodide Methyl Methacrylate 74-884 82WBIX'W 80-62-6 75-09-2 82WBIX W 8260BIX'W Methylene Chloride N-Butylbenzene 104-51-8 8260B LX~W -WP -Propylbi Naphtha 103-65-1 91-20-3 8260BIX'W 82fflBIX'W enzene alene Propionitrile Pyridine 107-12-0 8240B IX'W 110-86-1 10042-5 8260BIX'W 82«0B IX'W Styrene trans-1,2-Dichloroethene 156-60-5 8260B DC W trans-l,4-Dichloro-2-Butene Toluene 110-57-6 108-88-3 8260BIX: 8260B IX'W 8260B IX'W w^ 1,1,1,2- letrachloroethane 1,1,2,2- fetrachloroethane 630-20-6 79-34-5 127-184 8260B IX'W 82«0B IX'W Tetrachloroethene 1,2,3-1 richlorobenzene 87-61-6 8260B IX'W 1,2,4-Trichlorobenzene 1,1,2-Trichloroethane 120-82-1 79-00-5 8260B IX'W 8260B IX'W Trichloroethene 1,1,1 - rrichloroethane 79-01-6 8260BIX'W 71-55-6 75-694 8260B IX'W 8260B IX'W Trichlorofluoromethane 1,2,3-Trichloropropane 96-184 8260B IX'W opr 1,2,4-1 rimethylpenzene 1,3,5-1 rimethylbenzene 95-63-6 108-67-8 8260B1X"W 8260B IX'W Vinyl Acetate Vinyl Chloride' 108-054 8260B IX'W 75-014 1330-20-7 8260B IX'W 8260B IX'W m,p-Xyli o-Xyle 9547-6 8260B 1X"W ene Note: *Laboratory to filter sample with 0.2 um / -ia filitr l:-:o-c^: f '. CK ATKy5l278.00l/SLC5R03l Copyright 2005 Kleinfelder, Inc. Page 3 of 3 June 22, 2005 Table C-3 Injection Period and Post Injection Monitoring Period Partial Analytical List for Groundwater Samples Pilot Test Work Plan for Perchlorate Remediation ATK - Promontory Facility Analyte Nitrate-N Perchlorate* pH/ORP** Phosphoms (total) Phosphate Mel^^B:- IC 300.0 Anions Perchlorate 314 (IC) W 300.0 365 (IC) Note: •Laboratory to filter sample with 0.2 um **For field confirmation ATK/51278.001/SLC5R031 Copyright 2005 Kleinfelder, Inc. Page 1 of 1 June 22, 2005 CERTIFICATE OF ANALYSIS Listing of Sample Information and Testing Requested Monday, May 16, 2005 TESTED FOR: ATK Thiokol: DLV Environmental Monitoring MS 301 Thiokol Corp, UT 84322 ANALYZED BY: ATK Thiokol Propulsion Environmental Laboratory P.O. Box 707, M/S 245 Brigham City, UT 84302-0707 435-863-3732 435-863-8080 Contact Name: Project: Sample Delivery Group: John Holladay Ground Water Testing - DLV 0504008 Page 1 of 10 Sample Delivery Group: 0504008 Sample No. Client No. Test Requested Sample Description EPA 300.0 EPA 314.0 Anion Anatysis by IC Perctilorate - Ion Chromatography Received Collect Date/Time Matrix 0504008-01 EPA 160.1 EPA 160.2 EPA 300.0 EPA 300.0 EPA 310.1 EPA 314.0 EPA 340 2 EPA 350.1 EPA 350.1 EPA 376.1 EPA 410.4 1805158- SW 846, 9066 SW-846, 601 OB (Waler) SW-846, 8260B (Waler) 0504008-02 1805158- SW-846, 601 OB (Waler) 0504008-03 1S05158- 1871 Total Dissolved Solids Analysis Total Susperxjed Solids Analysis Chlorate by IC Anion Analysis by IC Alkalinity Analysis Perchlorate - lon Chromatography Fluoride/Ion Selective Electrode Ammonia Distillation Ammonia Analysis Dislillalion/Titrimetric COD Analysis Phenol (Distillation/Autoanalyzer) Metals Analysis by ICP - 6010 Volatile Organics Appendix 9 1871 (Total Meials - Unfiltered) 1172 Metals Analysis by ICP - 6010 04rt)7A)5 4/7/2005 11:05:04 Water Water Waler Water Water Water Water Water Water Water Water Wafer Water Water 04/07/05 4/7/2005 11:05:54 Waler 04/07/05 4/7/2005 12:55:54 Water Water ••^- 0 40 q^«'^ £_7 ^A<K\-\^^ /-/\!b/\ lc \^^ c Page 2 of 10 Sample Delivery Group: 0504008 Sample No. Client No. Test Requested 0504008-03 1S05158 - 1172 Sample Description Received Collect Date/Time Matrix 0*07/05 4/7/2005 12:55:54 SW-846. 8260B (Water) Volatile Organics Appendix 9 Water Certified By: v^"^^"^-^" Hf.MrS'. tpt^ W. Scott Fraser, Quality Assurance Officer 05/16/2005 Date This certifies that the following samples were analyzed using good laboratory practices to show the following results: Page 3 of 10 Listing of Results by Sampie Sample Delivery Group: 0504008 Client Sample ID: 1S05158 -1871 ,p. , Sample Description: ATK-DLV - Promontory Well B-6 Laboratory Sample ID: 0504008-01 Date Sampled: 04/07/05 11:05 CAS Numt)er ! tMtUetiiod: Teit Method: Teat Method: 7775-09-9 Test ilMhod: ; Test Hfethod: i Ttat tieOiod: ; TestUetliod: Test Method: TestMeOtod: 7664-41-7 ! test MeOiod: ] Test Method: Test Method: 108-95-2 Test Method: 7429-90-5 7440-38-2 7440-39-3 7440-43-9 7440-70-2 7440-47-3 7439-89-6 7439-92-1 7439-95-4 7440-09-7 7782-49-2 7440-22-4 7440-23-5 7440-66-6 Test Parameter Resutt Units El'AieO.I Total Dissotved Solids/^alysis TOTAL DISSOLVED SOLIDS 4180 mgrt. EPA 160.2 Tolal Suspended Solids Analysis TOTAL SUSPENDED SOLIDS EPA 300.0 CHLORATE EPA 300.0 CHLORIDE NITRITE-N BROMIDE NITRATE-N SULFATE EPA3ld.i Chlorate by IC Anion Analysis by IC 28.0 mg/L U mg/L 2080. U 7.1 4.9 196. mg/L mg/L mg/L mg/L mg/L AJkalinity Analysis ALKALINITY EPA3U0 PERCHLORATE EPA 340.2 FLUORIDE EPA 350.1 AMMONIA DISTILLATION 267. mg/L Perchlorate - lon Chromatography 42400 Fluoiide/lon Selective Electrode 2.2 Ammonia Distillation 2/2005 12:00 ug/L mg/L Ammonia Analysis Distillation/Titrimetric EPA 350.1 AMMONIA-N EPA 376.1 SULFIDE EPA 410.4 COD Analysis CHEMICAL OXYGEN DEMAND 0.14 J mg/L U mg/L 21. J mg/L SWS46,9066 PHENOL SW.t46, 6010B (Water) ALUMINUM ARSENIC BARIUM CADMIUM CALCIUM CHROMIUM IRON LEAD MAGNESIUM POTASSIUM SELENIUM SILVER SODIUM ZINC Phenol (DIstillalion/AutoarMityzer) U Metals Analysis by ICP - 6010 mg/L Dilution MDL EQL Factor Analyst Test Date 19.8 3.2 40 0.5 4.8 0.1 04 0.1 3 500 0.01 2000 0 03 500 0.03 0.68 10 0.009 0.15 30 0.03 PCI PCI JJH CS KEN KEN PCI PCI KEN 04/11/05 4 2 20 1 2 1 15 1 10 200 10 10 10 100 PCI JJH JJH JJH JJH JJH JJH 04/11/05 04/13/05 04/13/05 04/11/05 04/11/05 04/11/05 04/11/05 04/20/05 04/14/05 04/27/05 04/12/05 04/15/05 04/12/05 04/19/05 12 2 J 55.4 J 81.6 U 164000 177 1060 U 53100 45800 U U 1300000 29. J ug/L ug/L ug/L ug/L ugA. ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L 10 20 2 1 ISOO 10 20 20 10 100 30 1 15000 10 50 100 10 5 7500 SO 100 100 SO SOO ISO 5 75000 50 50 50 1 JMA JMA JMA JMA JMA JMA JMA JMA JMA JMA JMA JMA JMA JMA 05/11/05 05/11/05 05/11/05 05/11/05 05/09/05 05/11/05 05/11/05 05/11/05 05/11/05 05/11/05 .05/11/05 05/11/05 05/09/05 05/11/115 Page 4 of 10 Listing of Results by Sannple Sample Delivery Group: 0504008 Client Sample ID: 1S05158 -1871 Sample Description: ATK-DLV - Promontory WeU B-6 Laboratory Sample ID: 0504008-01 Date Sampled: 04/07/05 11:05 CAS Number test Metiiod: 87-64-1 107-02-8 107-13-1 107-05-1 71-43-2 108-86-1 74-97-5 75-27-4 75-25-2 74-83-9 71-36-3 78-93-3 135-98-8 98-06-6 75-15-0 56-23-5 108-90-7 75-00-3 110-75-8 67-66-3 74-87-3 126-99.8 95-49-8 106-43-4 108-94-1 96-12-8 124-48-1 106-93-4 74-95-3 95-50-1 541-73-1 106-46-7 75-34-3 107-06-2 75-35-4 156-59-4 75-71-8 78-87-5 142-28-9 590-20-7 563-58-6 10061-01-5 10061-02-6 141-78-6 100-41-4 60-29-7 97-63-2 76-13-1 87-68-3 591-78-6 67-63-0 Twt Par?in?t9r RWMH SiV^B<6, 82608 (VVafwJ Volatile Organics Appendi)r9 ACETONE ACROLEIN ACRYLONITRILE ALLYL CHLORIDE BENZENE BROMOBENZENE BROMOCHLOROMETHAN E BROMODICHLOROMETHANE BROMOFORM BROMOMETHANE 1-BUTANOL 2-BUTANONE SEC-BUTYLBENZENE TERT-BUTYLBENZENE CARBON DISULFIDE CARBON TETRACHLORIDE CHLOROBENZENE CHLOROETHANE 2-CHLOROETHYLVINYL ETHER CHLOROFORM CHLOROMETHANE CHLOROPRENE (2-CHLORO-1.3-BUTADIE 2-CHLOROTOLUENE 4-CHLOROTOLUENE CYCLOHEXANONE 1,2-DieROMO-3-CHLOROPROPANE DIBROMOCHLOROMETH/^E 1,2-DIBROMOETHANE DIBROMOMETHANE 1,2-DICHLOROBEN2ENE 1,3-DICHLOROBENZENE 1,4-DICHLOROBENZENE 1,1-DICHLOROETHANE 1,2-DICHLOROETHANE 1,1-DICHLOROETHENE CIS-1,2-DICHLOROETHENE DICHLORODIFLUOROMETHANE 1,2-DICHLOROPROPANE 1,3-DICHLOROPROPANE 2,2-DICHLOROPROPANE 1,1-DICHLOROPROPENE CIS-1,3-DICHLOROPROPENE TRANS-1,3-DICHLOROPROPENE ETHYL ACETATE ETHYLBENZENE ETHYL ETHER ETHYL METHACRYLATE 1.1.2-TRICHLORO-1,2,2-TRIFLUOROETHAI HEXACHLOROBUTADIENE 2-HEXANONE ISOPROPYL ALCOHOL U U U U 0.5 J U U U U U U U U U U U U U U 20.3 U U U U U U U U U U U U 7.2 J 1.3J 75.5 32.0 U U U U U U U U U U U U U U U yniti ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L liQL 30 4.65 16 0.5 0.22 0.37 0.31 0.19 0.42 0.57 5.2 1.11 0.16 0.2 0.13 0.27 0.16 0.35 1.71 03 0.81 0.9 0.24 0.15 1.56 0.35 0.18 0.15 0.25 5.86 5.62 5.88 0.49 0.29 0.16 0.16 0.66 0.16 0.24 0.9 0.17 0.4 0.18 0.63 0.16 0.2 0.19 1 0.9 07 3 Diiul EQL Eac 100 1 10 1 50 1 10 1 10 1 10 1 10 1 10 1 10 1 10 1 10 1 10 1 10 10 1 10 1 10 1 10 1 10 10 10 10 10 10 10 10 10 s 10 s 10 10 10 10 10 10 10 5 10 10 10 10 10 10 6.3 5 2 10 10 10 10 30 Ion tor Analyst LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH t LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH Test Date 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 Page 5 of 10 Listing of Results by Sampie Sample Delivery Group: 0504008 Client Sample ID: 1805158 -1871 Sample Description: ATK-DLV - Promontory Well B-6 Laboratory Sample ID: 0504008-01 Date Sampled: 04/07/05 11 05 Dilution CAS Number restitfeefiod: 98-82-8 108-10-1 78-83-1 79-46-9 99-87-6 126-98-7 74-88-4 80-62-6 75-09-2 104-51-8 103-65-1 91-20-3 107-12-0 110-86-1 100-42-5 156-60-5 110-57-6 108-88-3 630-20-6 79-34-5 127-18-4 87-61-6 120-82-1 79-00-5 79-01-6 71-55-6 75-69-4 96-18-4 95-63-6 108-67-8 108-05-4 75-01-4 1330-20-7 95-47-6 460-00-4 1868-53-7 17060-07-0 2037-26-5 Test Parameter SW-84S,i2S6B(Wlterf VolaMe Organics Ap ISOPROPYLBENZENE 4-METHYL-2-PENTANONE 2-METHYL-1-PROPANOL (ISOBUTYL ALCC 2-NITROPROPANE 4-ISOPROPYLTOLUENE METHACRYLONITRILE METHYL IODIDE METHYL METHACRYLATE METHYLENE CHLORIDE N-BUTYLBENZENE N-PROPYLBENZENE NAPHTHALENE PROPIONITRILE PYRIDINE STYRENE TRANS-1.2-DICHLOROETHENE TRANS-1,4-DICHLORO-2-BUTENE TOLUENE 1,1,1.2-TETRACHLOROETHANE 1.1.2,2-TETRACHLOROETHANE TETRACHLOROETHENE 1,2,3-TRICHLOROBENZENE 1,2,4-TRICHLOROBENZENE 1,1,2-TRICHLOROETHANE TRICHLOROETHENE 1,1,1-TRICHLOROETHANE TRICHLOROFLUOROMETHANE 1.2,3-TRICHLOROPROPANE 1.2,4-TRIMETHYLBENZENE 1,3.5-TRIMETHYLBENZENE VINYL ACETATE VINYL CHLORIDE m.p-XYLENE O-XYLENE BROMOFLUOROBENZENE DIBROMOFLUOROMETHANE 1.2-DICHLOROETHANE-D4 TOLUENE-D8 Pwwit pendix9 U U U U U U U U U U u u u u u 1.4 J u 05 J U u u U U 1.2 J 2070 202 U U U U U U U 0.2 J 97.3 93.1 933 98.4 Vntts ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L % % % % MDL O.SS 0.53 5.33 0.99 0.24 0.39 0.21 0.49 0.77 0.3 O.IS 4 0.39 25 0.17 0.34 0.6S 0.21 0.25 0.85 0.28 0.23 4.37 0.2S 0.71 0.16 0.25 0.33 0.19 0.29 0.13 0.3 1.6 0.18 EQL F9C1 _ . 10 1 10 1 10 1 10 1 10 1 5 1 5 1 S 1 10 1 10 1 10 1 10 5 1 250 1 10 10 10 5 10 10 10 10 10 10 10 10 5 10 10 10 10 10 10 5 tar Analyst LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH TOTtDat? 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 Client Sampie ID: 1S05158 -1871 (Total Metals - Unfiltered) Sample Description: ATK-DLV - Promontory Well B-6 Laboratory Sample ID: 0504008-02 Date Sampled: 04/07/05 11 05 Dilution CAS Numlier Test Method; 7429-90-5 7440-38-2 7440-39-3 7440-43-9 7440-70-2 Test Parameter SW44e, SOf 08 (Watei) ALUMINUM ARSENIC BARIUM C/VDMIUM CALCIUM Metals Analysis by ICP Result - 60l0 491 62. J 84.1 U 169000 Units ug/L ug/L ug/L ug/L ug/L MQL 10 20 2 1 ISOO EQL .._.. so 100 10 5 7500 Factor 1 1 1 1 50 Analyst JMA JMA JMA JMA JMA Test Date Page 6 of 10 05/11/05 05/11/05 05/11/05 05/11/05 05/09/05 Listing of Results by Sample Sample Delivery Group: 0504008 ^^im Client Sampie ID: 1805158 -1871 (Total Metals - Unfiltered) Sampie Description: ATK-DLV - Promontory Well B-6 Lalioratory Sampie ID: 0504008-02 Oate Sampled: 04/07/05 11 05 CAS Number ' rest Method: 7440-47-3 7439-89-6 7439-92-1 7439-95-4 7440-09-7 7782-49-2 7440-22-4 7440-23-5 7440-66-6 Test Parameter SW-146,60108 (Water) CHROMIUM IRON LEAD MAGNESIUM POTASSIUM SELENIUM SILVER SODIUM ZINC Metals Analysis by ICP - 6010 Result -6010 472 1910 U 54000 46900 U U 1330000 24. J Units ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L MDL 10 20 20 10 100 30 1 15000 10 EQL so 100 100 50 500 150 5 7SO0O SO Dilution Factor 50 1 Analyst JMA JMA JMA JMA JMA JMA JMA JMA JMA Test Date 05/11/05 05/11/05 05/11/05 05/11/05 05/11/05 05/11/05 05/11/05 05/09/05 05/11/05 Client Sample ID: 1805158-1172 £-"7 Sample Description: ATK-DLV - Promontory Well Laboratory Sample ID: 0504008-03 Date Sampled: 04/07/05 12:55 Dilution CAS Number Test Method: Test Method: Teat Melhod: 67-64-1 107-02-8 107-13-1 107-05-1 71-43-2 108-86-1 74-97-5 75-27-4 75-25-2 74-83-9 71-36-3 78-93-3 135-98-8 98-06-6 75-15-0 56-23-5 108-90-7 75-00-3 110-75-8 67-66-3 74-87-3 126-99-8 95-49-8 106-43-4 108-94-1 Test Parameter EPA 3O0.0 CHLORIDE NITRITE-N BROMIDE NITRATE-N SULFATE EPA 314.0 PERCHLORATE SW-t46.12608 (Water) ACETONE ACROLEIN ACRYLONITRILE ALLYL CHLORIDE BENZENE BROMOBENZENE Anion Analysis by IC Result 1930. U 38 4.8 183. Perchlorate - lon Chromatography 40200 Volatile Organics Appendix 9 BROMOCHLOROMETHANE BROMODICHLOROMETHANE BROMOFORM BROMOMETHANE 1-BUTANOL 2-BUTANONE SEC-BUTYLBENZENE TERT-BUTYLBENZENE CARBON DISULFIDE CARBON TETRACHLORIDE CHLOROBENZENE CHLOROETHANE 2-CHLOROETHYLVINYL ETHER CHLOROFORM CHLOROMETHANE CHLOROPRENE (2-CHLORO-1,3-BUTADIE 2-CHLOROTOLUENE 4-CHLOROTOLUENE CYCLOHEXANONE U U U U 0.5 J U U U U U U U U U U U U U U 21.3 U U U U U Units mg/L mg/L mg/L mg/L mg/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ugA. ugA. ugrt. ug/L ug/L ugA. ugA. ugA- ugA. ug/L ugA. MPL 2.4 0.1 04 0.1 3 500 30 - 4.65 16 0.5 0.22 0.37 0.31 0.19 0.42 0.57 5.2 1.11 0.16 0.2 0.13 0.27 0.16 0.35 1.71 0.3 0.81 0.9 0.24 0.15 1.56 EQL 10 1 2 1 15 2000 100 10 50 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Factor 100 10 10 10 100 500 Analyst JJH JJH JJH JJH JJH JJH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH Test Date 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/14/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 Page 7 of 10 Listing of Results by Sample Sample Delivery Group: 0504008 Client Sample ID: 1805158-1172 --- ^ Sample Description: ATK-DLV - Promontory Well J|f Laboratory Sample ID: 0504008-03 Oate Sampled: 04/07/05 12:55 Dilution CA? Number Test Method: 96-12-8 124-48-1 106-93-4 74-95-3 95-50-1 541-73-1 106-46-7 75-34-3 107-06-2 75-35-4 156-59-4 75-71-8 78-87-5 142-28-9 590-20-7 563-58-6 10061-01-5 10061-02-6 141-78-6 100-41-4 60-29-7 97-63-2 76-13-1 87-68-3 591-78-6 67-63-0 98-82-8 108-10-1 78-83-1 79-46-9 99-87-6 126-98-7 74-88-4 80-62-6 75-09-2 104-51-8 103-65-1 91-20-3 107-12-0 110-86-1 100-42-5 156-60-5 110-57-6 108-88-3 630-20-6 79-34-5 127-18-4 87-61-6 120-82-1 79-00-5 79-01-6 TestPar?m«ter Pe?«H SW-M6, J260B (Water) Volatile Organics Appendix 9 1.2-DIBROMO-3-CHLOROPROPAN E DIBROMOCHLOROMETHANE 1,2-DIBROMOETHANE DIBROMOMETHANE 1,2-DICHLOROBENZENE 1,3-DICHLOROBENZENE 1,4-DICHLOROBENZENE 1,1-DICHLOROETHANE 1,2-OICHLOROETH ANE 1,1-DICHLOROETHENE CIS-1,2-0ICHLOROETHENE DICHLORODIFLUOROMETHANE 1,2-DlCHLOROPROP/>>NE 1,3-DICHLOROPROPANE 2.2-DICHLOROPROPANE 1,1-DICHLOROPROPENE ClS-1,3-DICHLOROPROPENE TRANS-1,3-DICHLOROPROPENE ETHYL ACETATE ETHYLBENZENE ETHYL ETHER ETHYL METHACRYLATE 1,1,2-TRICHLORO-1,2,2-TRIFLUOROETHAI HEXACHLOROBUTADIENE 2-HEXANONE ISOPROPYL ALCOHOL ISOPROPYLBENZENE 4-METHYL-2-PENTANONE 2-METHYL-1-PROPANOL {ISOBUTYL /U.CC 2-NITROPROPANE 4-ISOPROPYLTOLUENE METHACRYLONITRILE METHYL IODIDE METHYL METHACRYLATE METHYLENE CHLORIDE N-BUTYLBENZENE N-PROPYLBENZENE NAPHTHALENE PROPIONITRILE PYRIDINE STYRENE TRANS-1.2-DICHL0R0ETHENE TRANS-1,4-DICHLORO-2-BUTENE TOLUENE 1,1,1,2-TETRACHLOROETHANE 1,1,2,2-TETRACHLOROETHANE TETRACHLOROETHENE 1,2,3-TRICHLOROBENZENE 1,2,4-TRICHLOROBENZENE 1.1,2-TRICHLOROETHANE TRICHLOROETHENE U u u u u u u 8.1J u 181 36.9 U U U U U U U U U U U U U U U u u u u u u u u u u u u u u u u u u u u u u u 1.1 J 2300 Units ugA. ugA. ugA. ug/L ugA. ug/L ugA. ugA. ugrt. ugA. ugA. ugA. ugA. ugA. ug/L ugA. ug/L ugA. ug/L ug/L ug/L ug/L ugA. ugA. ugA. ugA. ugA. ug/L ug/L ugA. ugA. ugA. ugA. ugA. ugA. ugA. ug/L ugA. ugA. ugA. ugA. ugA. ugA. ugA. ugA. ug/L ug/L ug/L ug/L ug/L ugA. MDL 0.35 0.18 O.IS 0.25 5.86 5.62 5.88 0.49 0.29 0.16 0.18 0.66 0.16 0.24 0.9 0.17 0.4 0.18 0.63 0.16 0.2 0.19 1 0.9 0.7 3 0.58 0.S3 S.33 0.99 0.24 0.39 0.21 0.49 0.77 0.3 0.15 4 039 2S 0.17 0.34 0.6S 0.21 0.25 0.85 028 0.23 4.37 0.25 0.71 EQL Factor Analyst 10 1 5 1 10 1 5 1 10 1 10 1 10 1 10 1 10 1 10 1 10 1 5 1 10 1 10 1 10 1 10 1 10 1 10 1 6.3 1 5 1 2 1 10 1 10 10 10 30 10 10 10 10 10 5 5 S 10 10 10 10 s 250 10 10 10 S 10 10 10 10 10 10 10 LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH Test Date 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 Page 8 Of 10 Listing of Results by Sample Sample Delivery Group: 0504008 Client Sample ID: 1805158 - 1172 Sample Description: ATK-DLV - Promontory Well I e-7 Laboratory Sample ID: 0504008-03 Oate Sampled: 04/07/05 12:55 CAS Number Test Method: 71-55-6 75-69-4 96-18-4 95-63-6 108-67-8 108-05-4 75-01-4 133O-20-7 95-47-6 460-00-4 1868-53-7 17060-07-0 2037-26-5 T^st Parameter Result SW-t48, t2S0B (Water) Volatile Organics Appendix 1,1,1-TRICHLOROETHANE TRICHLOROFLUOROMETHANE 1,2,3-TRICHLOROPROPANE 1,2,4-TRIMETHYLBENZENE 1,3,5-TRIMETHYLBENZENE VINYL ACETATE VINYL CHLORIDE m.p-XYLENE O-XYLENE BROMOFLUOROBENZENE DIBROMOFLUOROMETHANE 1,2-DICHLOROETHANE-D4 TOLUENE-D8 9 201 U U U U U U U U 99.6 966 94.0 101 Vnit? ug/L ugA. ug/L ug/L ugA. ugA. ugA. ugA. ugA. % % % % Dilution MDL EQL Factor Analyst Test Date 0.16 0.25 0.33 0.19 0.29 0.13 0.3 1.6 0.18 . 10 1 5 1 10 10 10 10 10 10 5 LSH LSH LSH LSH LSH LSH LSH LSH 1 LSH 1 LSH 1 LSH 1 LSH 1 LSH 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 04/11rt)5 04/11/05 04/11/05 04/11/05 04/11/05 04/11/05 Page 9 OflO Data Reporting Qualifiers U Indicates that the analyte was not detected, or the analyte was detected but was below the MDL. B This flag is used when an analyte is found in the blank as well as the sample. Indicates an extimated value. This flag is used either when estimating a concentration for tentatively identified compounds or when the data indicated the presence of a compound that meets thd identification criteria but the result is less than the EQL (e.g. 3 J with an EQL of 10). MDL Method Detection Limit: The minimum concentration of a substance that can be confidently measured and reported. The laboratory has demonstrated that the MDL can be achieved in a laboratory reagent blank, but does not guarantee it can be achieved in all sample matrices. EQL Estimated Quantitation Limit: The EQL generally is Sto 10 times the MDL. For many analytes the EQL is selected as the value ofthe towest standard in the calibration curve. Dilution Dilution Factor: The prepared sample was diluted by this factor because the Factor sample was too concentrated or due to other interferences in the sample matrix. Any dilution factor causes a corresponding increase in the MDL and EQL. Page 10 of 10 ATK Thiokol, Inc. Environmental Laboratory 0S0^^t>2> Clianl Name Carrier:. Sample Receipt Checldist O Hand delivered, no cooler Q Hand delivered, sample<s) taken oul at receiving counter SDG No t/;>i/fu'iyv ffA 0 counter ODamaged toxplain) Seal Number Othar: Cooler Information: Cooler Number/IO: gf<^ i lJk,^c Condition of SNpping Container: Cooler Sealed (taped). Cusiody Seals Present Coolant: State ol Coolant: J^Sood QYes QYes Qlntact (frozen QFair flt*o QBroken OBlue Ice CX4one i3Pariially Frozen QNot/AppUcable ONot Applicable QNot Applicable QMelted Thermometer ID: HfSI'St Vf Reading: I */ -C CF: Corrected Temp;. Pac.ngD.sc.ip.on: /"^^ ^. A -T^^ ^.> fJ JC Tonp Blai* Included. QYes QNo CluhvOf-Custody Information COC Present: - ^ COC Numbef(sl: ^ ft AYes COC signed (relinquished and rece«ved): ^es COC agrees with sample labels: ^es QNo QNo QNo Notes:. Other. ONol Applicabie ONot Applicable Sample Infonnation: Samples included in cooler: <^Sc?Ye?c?^ Custody Seals Present: Sample conlainers intact: Samples in proper conlainers: Suffident sample volume: Al samples received in hold time: QYes anlact ,«n'es *?es J*yes .SYes Water - VGA's have zero headspace: j^e-presen^ed with HCl: Notes: 1^0 Othor. QBroken Seal Numberfs). QNo Notes: CHa QNo QNo ^___ ^es ar4o QNot Applicable QPre-preserved with Na^SiO.: 04on-Presen/ed: Water-pH acceptable upon receipt: J^es QAdjusted (see comments below) QNot Applicable HNO, - ^ t' H,SO, = ^ Z NaOH . -^ ^^ ZnAC /NaOH . T' i'^ _HCL = . Water - pH ad|usted: (mfg & Lot No.) HNO, HjSO, NajSOjO, Other. Notes -NaOH. _ZnAC. HCl ^i9f(^j^c^ ~)*^eUf ^euc^aU. vo»^ a.cttff/i^^ Sff». ^f-C. /*A-c yc e*t u-^^ /^• ?A«»y/"<; U/a,f /*, li^t^^J ^^«- ,r^^uj.f / a-T Ctr,'< /Su-e^. 4 . ATK ATK Thiokol, Inc. P.O. BOX 98, MAGNA, UTAH 84404 4/6/2005 GENERAL INFORMATION LAB: ATK ORDER No: 984PLS33H««'^lv PROJECTNO: 98BP-3 COLLECTED BY: Chris Busch COLLECTION LOCATION: Promontory Well B-6 MATERIAL SAMPLED: Groundwater CONTACT: Chris Busch TEL: 801-251-3562 FAX: 801-251-5750 SAMPLE INFORMATION Note: Page 1 of 2 I I I I CHAIN OF CUSTODY RELINQUISHED BY ^<U /^ A RECEIVED BY DATE TIME y/7/^^ T^W