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HomeMy WebLinkAboutDSHW-2007-002419 - 0901a0688013e0acLauicl: Sysieois Gfcup P.O. Box 98 """'"'"""" HAND DELIVERED wwvv.rilk.coiii APR 1 8 2007 UTAH DIVISION OF SOLID & HAZARDOUS WASTE April 18,2007 _ ,. Dennis R. Downs, Director Department of Environmental Quality Division ofSolid and Hazardous Waste 288 North 1460 West P.O. Box 144880 Salt Lake City, Utah 84114-4880 RE: ATK Launch Systems Inc., EPA ID# UTD009081357 Flow Cell Treatability Study Dear Mr. Downs, ATK Launch Systems Inc. (ATK) is submitting a notification to the Division of Solid and Hazardous Waste to conduct a Flow Cell Treatability Study (the Study). The purpose of the Study is to investigate altemative electron donor sources and delivery practices for the ATK Bacchus Bioremediation Pilot Plant. A copy of the Study is attached. If you have questions or need additional information conceming this Study, please contact Paul V. Hancock at (435) 863-3344. Sincerely, David P. Gosen, P.E. Director, Environmental Services .ATK Launch SvsK'ins Envimnnicnliil Services Bacchus Enhanced In Situ Bioremediation Pilot Plant Biofilm Control: Flow Cell Treatability Study Design Fourth Revision - Draft J.E. Wells ATK Launch Systems Environmental Services February, 2007 J.E.Wells Paee 1 4/18/2007 .AIK Luunch .Svsicin.s l.-.iiviionnii.-nuil ScrvicL-s Abstract A bench-scale flow cell reactor is being constructed to study microbial biofilm control. The purpose of this study is to investigate altemative electron donor sources and delivery practices that may alleviate biofouling. This study will also investigate which electron donor feed methods work best to minimize biofouling. Introduction Well biofouling is a common concem when using enhanced in situ bioremediation (EISB) technology to treat contaminated groundwater. Left uncontrolled, biofilm proliferation in electron donor injection wells have the capability to upset the system by impeding (i.e. generation of backpressure) groundwater recharge. Such a scenario has been encountered at the Alliant Techsystems' Bacchus facility. An EISB pilot plant operating on the facility to remediate perchlorate contaminated groundwater has been ineffective due to significani biofouling. The purpose of this study is to investigate altemative electron donor sources and delivery practices that may alleviate biofouling. Ethanol and citric acid have previously been used in the Bacchus EISB plant as electron donors with negligible success. In both cases, the recharge well was fouled with a stable biofilm unaffected by chlorine dioxide injections used to kill or inhibit bacterial growth. Ethanol and citric acid are readily metabolized by the microbial community either directly or indirectly; leading to a significant portion ofthe community being stimulated. This leads to an environment where rapid growth rates and survival mechanisms are essential for a particular population to proliferate. Depending on the conditions, there is an opportunity for nondesirable or "weedy" bacteria to outcompete more desirable populations. Therefore, as suggested by Coates et al, utilizing compounds that are metabolized by limited populations in the community is expected to be more effective. Electron donor can be added to groundwater through a single injection batch feed or a continuous feed. There is no clear answer as to which delivery regimen is the most beneficial to prevent fouling. A strong batch delivery of an electron donor with biocide or biofilm dispersal activity would seem to have the greatest effect in preventing biofilm foiTnation on the injection well screen. However, depending on retention time in and around the well screen, a lagging interface (as the concentrated "plug" of donor passes out of the screen) of electron donor that has dropped below the inhibitory concentration might develop and lead to rapid biofilm foiTnation over subsequent injections. Altematively, the theory of a continuous feed system is to maintain a constant flow of electron donor at relatively low concentration to limit biomass production. The success of this type of delivery may depend on keeping concentrations of electron donor and an additional biocide amendment (i.e. chlorine) at levels necessary to prevent initial biofilm formation. If biofilm formation becomes established, significant fouling could result. This study will investigate which feed method works best for the electron donors under investigation. J.F:. Wells .Paee 2 4/18/2007 .ATK l.;)uni.ii Svslciiis l:n\ iioniiK-riMl Scr\ ices Hypothesis The hypotheses tested by this study are stated below: Null donors: No differences in biofilm formation are observed between altemative electron donors and citric acid. Null delivery: No differences exist between continuous delivery and batch delivery of electron donor. Bacchus Groundwater Chemistry Table 1 shows the values for particular constituents of interest in the Bacchus groundwater. These values have been used to calculate electron donor demand for microbial mediated perchlorate reduction and determine water hardness. TABLE 1. Bacchus Groundwater Constituents of Interest Constituent Perchlorate Calcium Magnesium Nitrate Dissolved Oxygen mg/L 0.3 35* 10* 18 8 Values from Magna Water Company "Water Quality Report for 2005" Flow Cell Design Figure 1 illustrates the schematics for the flow cell. The system is loosely a 1/16 scale model of the Bacchus EISB plant. Tubing diameters and exit flow rate from the well screen are modeled as accurately as possible. Unlike the EISB plant, the flow cell relies on continuous recirculation through three 5 gallon reservoirs to model approximately 24 hours of retention time. The retention time is obtained by circulating approximately 33 liters of groundwater from the Bacchus EISB plant at a constant flow rate of 20 mL/min. The low flow rate models the outflow of injected groundwater through the well screen's open surface area. To compensate for groundwater constituent loss (i.e. nitrate, perchlorate) during recirculation, a concentrated nitrate/perchlorate feed solution and oxygen will be pumped into a "recharge reservoir" continuously. The following is a description for each component in the flow cell: J.r-. Wells Paee 3 4/18/2007 .ATK l.uuncli ,S\sK'itis l-'.n\ n-i.jnuKMU.il .Sci\ici^s Feed Reservoir: The reservoir is a 5 gallon polypropylene container with lid. This reservoir contains the circulation pump and acts as a recharge reservoir. Perchlorate, nitrate and dissolved oxygen (via an aquarium pump) will be added at the top of the reservoir to bring the water back to pretreatment conditions. Sample Reservoir: The reservoir is a 5 gallon polypropylene container with lid. Receives water via gravity flow from the Holding Reservoir. Water will be collected from an oveiflow tube at the top of the reservoir and analyzed for perchlorate and electron donor concentrations. Holding Reservoir: The reservoir is a 5 gallon polypropylene container with lid. Receives water that has been amended with electron donor and has flowed through the Biofilm Attachment Surface and Groundwater Recirculation Line. The holding reservoir allows for extended retention time for perchlorate reduction. Circulation Pump: The circulation pump is a Dayton 1/100 hp compact submersible centrifugal pump rated to 240 GPH at 1 foot of head. This will provide continuous flow through the system. Donor Feed Reservoir: The donor feed reservoir is a 1 gallon aspirator bottle designed to deliver electron donor to the flow cell. The flow from the Donor Feed Reservoir is controlled by a fluid metering pump that pressurizes the aspirator bottle and displaces the appropriate volume. The donor feed rate is calibrated to deliver the maximum per day donor requirements for each treatment (0.170 L/day for each cell). Biofilm Attachment Surface (BAS): This component is made of !^" Schedule 80 clear PVC pipe. The pipe is 30 inches long to simulate the 40 foot well screen at the EISB plant. The clear PVC allows for biofilm observations during flow cell operation. Groundwater Feed/Recirculation Line: These lines are made of '/i" outer diameter (0.170" inner diameter) polyethylene tubing rated to 150 psi. The lines are used to simulate the two inch lines at the EISB plant that deliver water from the extraction wells to the recharge well. A valve connected to the end of the Recirculation Line provides the 20 mL/min flow rate through the system. Nitrate / Perchlorate Feed Reservoir: This reservoir will be used to deliver a concentrated perchlorate/nitrate feed solution to maintain a steady state concentration in the recirculated groundwater. The concentrated solution recharges the recirculated groundwaler to simulate the continuous flow of untreated water that comes into the EISB plant. One variable rate metering pump will be used to deliver perchlorate/nitrate solution to the feed reservoir of all five flow cells at 0.17 L/day (0.118 mL/min continuous delivery). The calculation is shown below: Potassium Nitrate 18 mg/17day x 33 L = 594 mg/day x 21 days = 12474 mg x 5 cells = 62370 mg 0.17IVday flow rate x 5 cells = 0.85 L/day x 21 days = 17.85 L J.il Wells Page 4 4/18/2007 .ATK I ;iiuu:h .S\'sli.'m:S Fin ironmcnial .Services KJMO3 atomic mass/NOa' atomic mass = 101 grams per mole /62 grams per mole = 1.63 1.63 X 62370 mg NO3" = 101,663 mg KNO3/I7.85L Note: 17.85 L is near container capacity for "5 gallon " reservoirs. Ammonium Perchlorate 0.3 mg/I7day x 33 L =10 mg/day x 21 days = 210 mg x 5 cells = 1050 mg 0.17lVday flow rate X 5 cells = 0.85 Udayx 21 days = 17.85 L NH4CIO4 atomic mass/C104' atomic mass =117 grams per mole/99 grams per mole = 1.18 1.18 X 1050 mg CIO4" = 1239 mg NH4CIO4/I7.85L Note: 17.85 L is near container capacity for "5 gallon " reservoirs. Figure 1. Flow Cell Schematic Jr \ t Flow Conlrol Valve Holding Reservoir To Overflow Proledion Reservoir fc>n Flow Conlrol Valve Overtlow Perchlorale/Nilraic Feed Reservoir Overflow/sample lube Pressure Groundwaler _f ^ Feed t Sample Reservoir T)M Groundwater Recirculation Line Donor Feed Reservoir w/pump J.L. Wells Paee 5 4/18/2007 .A'l'K l.uunch Svslciiis •.ii\ iionnicnuil .Scr\ ices Study Treatments The Flow Cell study is comprised of three electron donor treatments and a positive and negative control. Each trealment will be studied for 21 days. The treatments and controls are shown in Table 2. Table 2. Flow Cell Treatments Treatment 1 2 3 Positive Control Negative Control Electron Donor Nitrilotriacetic Acid (NTA) Socdium Benzoate (SB) NTA/SB Citric Acid No Donor Treatment 1: Nitrilotriacetic Acid Nitrilotriacetic Acid (NTA) is a chelant similar lo elhylenediaminetelraacetic acid (EDTA). Chelants have been used previously (specifically EDTA) in medical device research to disperse P. aeruginosa biofilms (Banin et al, 2006). Additionally a calcium-specific chelant, ethylene glycol-bis (P-aminoethyl ether)-A/,A^-tetraacetic acid (EGTA), was shown to disperse mixed population biofilms derived from activated sludge (Turakhia et al, 1983). The effectiveness of these chelants is related to their ability to remove free calcium and magnesium cations which are known to affect "slime" formation. The significant advantage of NTA is that it is readily biodegradable compared lo EDTA. In fact, a Pseudomonas sp. was shown to utilize NTA as a sole carbon source (Bourquin et al, 1977). Furthermore, a more recent report showed a denitrifying bacterium capable of using NTA as a sole carbon source while using NO3" as the terminal electron acceptor in an anaerobic environmeni (Jenal-Wanner et al). These findings beg the question of whether members of the perchlorate reducing community in a groundwater environment may be able to use NTA as an electron donor during perchlorate reduction. NTA has two appealing properties as a candidate for biofouling control. As a chelant, it is capable of reducing free calcium and magnesium cation concentralions. Therefore, NTA should act as a deterrent to biofilm formation al suitable concenlralions. As an electron donor, NTA is metabolized via specific pathways that are mosl likely nol preseni in all members of the groundwater microbial community. Moreover, since some denitrifying bacteria have been shown lo posses such pathways, it is hopeful that NTA would also be metabolized directly by some perchlorate reducing bacteria. Thus, unlike ethanol or citrate that are metabolized by a wide array of bacteria (eilher directly or indirectly); NTA may provide the ability to better target desired populations in the communiiy. The NTA demand for perchlorate reduction was calculated using the values for perchlorate, nitrate and dissolved oxygen shown in Table 1. The balanced redox reaction and stoichiometric ratio are shown below for each constituent: Perchlorate 4C6H6N06Na + 9CIO4" -1- 12 H^ —• 24C02 + 9Cr -I- 12Na^ -1- 4NH3 -1-I2H2O Stoichiometric ratio: Molecules NTA x atomic mass NTA = 4 x 257 = 1.15 J.F.. Wells Paee 6 4/18/2007 .ATK l.aunch S>slciiis Einiionnieni.il .Services Molecules CIO4' x atomic mass CIO4" 9 x 99 Nitrate 5C6H6N06Na + 18NO3" + 33H^ • 3OCO2 -f- 9N2 -1- 15Na^ + 5NH3 + 24H2O Stoichiometric ratio: Molecules NTA x atomic mass NTA = 5 x 257 = 1.15 Molecules NO3" x atomic mass NO3" 18 x 62 Dissolved Oxygen 2C6H6N06Na + 9O2 + 6H^ • 12CO2 + 6Na^ -1- 2NH3 + 6H2O Stoichiometric ratio: Molecules NTA x atomic mass NTA = 2 x 257 = 1.78 Molecules O2 x atomic mass O2 9 x 32 Final stoichiometric demand using NTA as an electron donor is illustrated in Table 3: Table 3. NTA Electron Donor Demand Constituent Demand Perchlorate Nitrate Dissolved Oxygen (0.300 ppm X 1.15 stoichiometric ratio) x 1.25 excess = 0.431 ppm NTA (18 ppm X 1.15 stoichiometric ratio) x 1.25 excess = 26 ppm NTA (8 ppm x 1.78 stoichiometric ratio) x 1.25 excess = 18 ppm NTA Total 45 ppm NTA The quantity of NTA needed for a 21 day study is calculated below: 45 mg/L NTA x 33 L Groundwater = 1485 mg NT A/day x 21 day = 31185 mg NTA A 34 mM solution (8684 mg/L or 33g/3.8L) of NTA will deliver the required mass al a flow rateof 0.17L/day: 45 mg/L NTA x 33 L Groundwater = 1485 mg NTA/day/8684 mg/L = 0.17 L/day Note: The 45 ppm electron donor demand for NTA also creates a 1:1 chelator to calcium/magnesium ion ratio. Trealmenl 2: Sodium Benzoate Sodium Benzoate (SB) is commonly used as an antimicrobial in processed foods. Generally, SB becomes inhibitory al concentralions greater than 1000 ppm and pH values less lhan 5. SB is readily degraded in bolh aerobic and anaerobic environments. Although SB has an inhibitory effecl on bacteria, the ability lo maintain necessary concentrations and an effeclive J.H. Wells Paee 7 4/18/2007 .\TK l.aiincli .Svslenis Hiuimrinicnial Services pH while maintaining the proper levels for perchlorate reduction become limiting faclors. Furthermore, SB may not have an inhibitory effecl on some organisms in a diverse groundwaler microbial communiiy. Nevertheless, like NTA, SB is metabolized by bacteria with specific enzymes that allow for the molecule lo be broken down inlo functional intermediates. Therefore, a portion of the microbial communiiy is directly stimulated. This can include the targei perchlorate reducers. A perchlorate reducing Dechloromonas strain was found lo degrade benzene anaerobically wilh perchlorate as the terminal electron acceptor (Chakraborty et al, 2005). Perchlorate 4C7H502Na+15C104'-t-4H^ —• 28CO2-i-15Cr-f-4Na^-(-4NH3-1-I2H2O Stoichiometric ratio: Molecules SB x atomic mass SB = 4 x 144 = 0.39 Molecules CIO4" x atomic mass CIO4" 15 x 99 Nitrate C7H502Na-I-6NO3" + 7H^ • 7CO2-t-3N2-t-Na*-1-6H2O Stoichiometric ratio: Molecules SB x atomic mass SB = 1 x 144 = 0.39 Molecules NO3' x atomic mass NO3" 6 x 62 Dissolved Oxygen 2C7H502Na + 15O2 -I- 2H* • 14CO2 -1- 2Na* + 6H2O Stoichiometric ratio: Molecules SB x atomic mass SB = 2 x 144 = 0.6 Molecules O2 x atomic mass O2 15 x 32 Final stoichiometric demand using SB as an electron donor is illustrated in Table 4: Table 4. Sodium Benzoate Electron Donor Demand Constituent Demand Perchlorate Nitrate Dissolved Oxygen (0.300 ppm x 0.39 stoichiometric ratio) x 1.25 excess = 0.146 ppm SB (18 ppm X 0.39 stoichiometric ratio) x 1.25 excess = 8.8 ppm SB (8 ppm X 0.6 stoichiometric ratio) x 1.25 excess - 6 ppm SB Total 15 ppm SB The quanlily of SB needed for a 21 day study is calculated below: 15 mg/L SB X 33 L Groundwater = 495 mg SB/day x 21 day = 10395 mg SB J.E. Wells Paee 8 4/18/2007 .A TK Launch .Svsleins r.uviiunmcnial Seivues A 20 mM solulion (2895 mg/L or llg/3.8L) of SB will deliver the required mass al a flow rate of 0.17L/day: 15 mg/L SB X 33 L Groundwater = 495 mg SB/day/2895 mg/L = 0.17 L/day Trealmenl 3: NTA/SB Mixture A likely scenario is a mixlure of both SB and NTA. NTA's potenlial lo deter biofilm formation by the reduction of free calcium and magnesium cations is a significant attribute. However, il is unknown how well il might function as a sole electron donor or what microbial populations might be specifically stimulated. SB's biocide properties are limiied lo concentrations and pH levels that are mosl likely undesirable and difficult lo achieve (high concentration to achieve biocidal properties in excess of demand). On the olher hand, SB has been shown to be metabolized directly via perchlorate reduction; allowing for the hope for specific stimulation of perchlorate reducers. A 50/50 combination of NTA and SB will be used lo study the combined effects. Positive Control: Citric Acid Citric acid has previously been used as an electron donor at the EISB and generaied significani biofouling in the recharge well (RW-1). Therefore, it is being used as the positive conlrol in this study to evaluate if the flow cell design and the waler chemistry support the same extent of biofouling previously observed. Perchlorate 4C6H807-I-9C104' —• 24C02-l-9Cr+I6H2O Stoichiometric ratio: Molecules Citric Acid x atomic mass Citric Acid = 4 x 192 = 0.86 Molecules CIO4" x atomic mass CIO4' 9 x 99 Nitrate 5C6H8O7 -I- I8NO3" -I- 18H* • 3OCO2 + 9N2 -I- 29H2O Stoichiometric ratio: Molecules Citric Acid x atomic mass Citric Acid = 5 x 192 = 0.86 Molecules NO3" x atomic mass NO3" 18 x 62 Dissolved Oxygen 2C6H8O7 + 9O2 -I- 2H* • i2C02 + 8H2O Stoichiometric ratio: Molecules Citric Acid x atomic mass Citric Acid = 2 x 192 = 1.33 Molecules O2 x atomic mass O2 9 x 32 J.F. Wells Paee 9 4/18/2007 .ATK l.aLincli Svslciiis P.iniinninenial Ser\ lee^ Final stoichiometric demand using SB as an electron donor is illustrated in Table 5: Table 5. Citric Acid Electron Donor Demand Constituent Demand Perchlorate Nitrate Dissolved Oxygen (0.300 ppm x 0.86 stoichiometric ratio) x 1.25 excess - 0.332 ppm Citric Acid (18 ppm X 0.86 stoichiometric ratio) x 1.25 excess = 19.4 ppm Citric Acid (8 ppm X 0.6 stoichiometric ratio) x 1.25 excess = 13.3 ppm Citric Acid Total 33 ppm Citric Acid The quanlily of citric acid (CA) needed for a 21 day study is calculated below: 33 mg/L CA X 33 L Groundwaler = 1089 mg CA/day x 21 day = 22869 mg CA A 33 mM solulion (6315 mg/L or 24g/3.8L) of CA will deliver the required mass al a flow rateof 0.17L/day: 33 mg/L CA X 33 L Groundwater = 1089 mg CA/day/6315 mg/L = 0.17 L/day Negative conlrol: No Donor This trealmenl allows for biofilm formation observations lo be laken when no donor is preseni. The negative control provides a measure of biofilm formation due to intrinsic groundwater properties. Continuous vs Batch Delivery To study the impacl of electron donor delivery rale on biofilm formation, the flow cell for each treatment will be operated in both a continuous and batch delivery configuration. Continuous delivery provides a low concentration environmeni in the BAS where electron donor is always present. The electron donor feed pump will be calibrated to deliver donor al a consistent 0.118 mL/min feed rale lo achieve the 0.17 L/day donor requiremenl. Alternatively, a batch delivery configuration provides an environmeni in the BAS where donor is preseni for only a short period of time but at high concentrations. For this configuration, the electron donor feed pump will be calibrated to inject the 0.17 L daily requiremenl in a single timed injeciion. Sample Collection Wells Page 10 4/18/2007 .ATK l.aunch Svslciiis Envi ron nicnial Services Water samples will be collected from the discharge hose that connects the Sample Reservoir to the Feed Reservoir. Waler collected al this point will have been retained in the cell approximaiely 24 hours afler electron donor addition. The first sample from each cell will be taken circa 24 hours afler the study has been initiated. Dissolved oxygen and oxidation- reduction potential (ORP) in the Sample Reservoir will be monitored daily to determine when the second sampling should occur. Once Oxygen and ORP have reached suitable levels for perchlorate reduction (DO < 2 mg/L and ORP < 100 mV), a second sample will be laken from each cell. Subsequeni samples for laboratory analysis will be taken once per week or as deemed necessary. Approximaiely 300 to 340 mLs of water will be sampled for perchlorate, nitraie and electron donor. Safety Requirements Special care will be laken to ensure personnel working wilh or around the flow cells are nol exposed lo hazardous conditions. Placards will be in place indicating the chemicals in use and their concentrations as well as the HazCom Web MSDS number as shown in Table 6. All personnel working wilh the flow cells under experimental conditions will be required lo wear safety glasses with side shields, smock and natural rubber latex gloves. In addilion, to prolecl againsi electrical shock, all electrical devices will be connected lo an appropriale ground fault circuit interrupter (GFCI) as directed by ATK Safely. Additional requirements TABLE 6. Chemicals Planned for Flow Cell Experiments: MSDS Information Chemical Name Ammonium Perchlorate Citric Acid Nitrilotriacetic Acid Polassium Nitrate Sodium Benzoate HazComWeb MSDS # 6116 17449 17448 17450 17447 may be added as deemed necessary by ATK Safety. Post Study Material Disposal All waler and rinse water used in this study will be disposed of by processing ihrough the perchlorate bioreactor al Promontory's M705 treatment facility. Conlainers, tubing and other components ofthe flow cell will be triple rinsed before slorage or disposal. Summary Allemative electron donors that specifically largel the perchlorate reducing microbial population should be preferred over more generalisl donors such as ethanol and citric acid. Also, electron donors that inlerfere wilh biofilm formation are expected lo provide addilional advantages. NTA and SB both have these attributes. In addition, their potential as a mixture is appealing. This bench scale study evaluates the effectiveness of NTA, SB and SB/NTA lo limil biofouling while also stimulating microbial perchlorate reduction. In addilion, the study will investigate the most effeclive delivery means for each of the donor treatments. Finally, the flow cell reactor syslem can be utilized for fulure evalualion of biofilm conlrol agenis as needed. J.F. Wells Paee 1 1 4/18/2007 .ATK l.aunch Svslcms Hnvironiiicnial Services Works Cited Banin, E., K.M. Brady, E. P. Greenberg. 2006. Chelalor-Induced Dispersal and Killing of Pseudomonas aeruginosa Cells in a Biofilm. Appl. Environ. Microbiology. 72: 2064-2069. Turakhia, M.H., K.E. Cooksey, W.G. Characklis. 1983. Influence ofa Calcium-Specific Chelant on Biofilm Removal. Appl. Environ. Microbiology. 46: 1236-1238. Bourquin, A.W., V.A. Przybyszewski. 1977. Distribution of Bacteria with Nitrilotriacetale- Degrading Potential in an Estuarine Environmeni. Appl. Environ. Microbiology. 34: 411-418. Jenal-Wanner, U., T. Egli. 1993. Anaerobic Degradation of Nilrilotriacetate (NTA) in a Denitrifying Bacterium: Purification and Characterization of the NTA Dehydrogenase-Niirate Reductase Enzyme Complex. Appl. Environ. Microbiology. 59: 3350-3359. Chakraborty, R., S.M. O' Connor, E. Chan, J. D. Coates. 2005. Anaerobic Degradation of Benzene, Toluene, Elhylbenzene, and Xylene Compounds by Dechloromonas Strain RGB. Appl. Environ. Microbiology. 71: 8649-8655. Coates, J.D., L.A. Achenbach. Chapler 11. The Microbiology of Perchlorate Reduction and ils Bioremedialive Application. www.science.siu.edu/microbiology/achenbach/Chaplerl2_2005.pdf J.H.Wells Page 12 4/18/2007