DWQ-2024-004888

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Utah Lake Sediment Phosphorus Binding

Literature Review

Joshua J. LeMonte, Gregory T. Carling

Department of Geological Sciences, Brigham Young University

Submitted to Utah Division of Water Quality
December 2023

Final Revision Submitted March 2024

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1 Executive Summary

This literature review was prepared to contribute to the Utah Lake Water Quality Study
(ULWQS). Whereas comprehensive literature reviews were previously compiled during
earlier stages of the ULWQS, this literature review has a more specific topic: phosphorus
(P) sorption, or, binding, in Utah Lake. This additional review serves to directly supplement
other literature reviews conducted as part of the ULWQS.1,2 Specifically, this review
provides additional literature sources that are applicable to the ULWQS Charge Question
2: “What is the current state of the lake with respect to nutrients and ecology”? More
specifically, this review addresses Charge Question 2.3.5: “What is the role of calcite
“scavenging” (i.e. binding) in the phosphorus cycle”?

The objective of this literature review is to explore the factors that influence P retention
and release across the water column—sediment interface in Utah Lake, a large, alkaline,
eutrophic basin-bottom shallow lake. These factors are presented broadly first, followed
by specific findings and applications regarding Utah Lake. Phosphorus cycling in lakes
and shallow lakes is introduced, followed by a discussion regarding P dynamics in the
water column and finally P retention and release in lakebed sediments is reviewed. Within
each of these sections, a broad introduction of the processes precedes specific
applications to the Utah Lake system. Additionally, methods used to parameterize these
processes are presented.

This review was conducted by searching peer-reviewed literature, books and book
chapters, and public reports using Web of Science (www.webofknowledge.com) and
Google Scholar (www.scholar.google.com), with search terms and parameters saved in
order to auto-update as new manuscripts are published. Search term keywords included:
P, speciation chemistry, Utah Lake, scavenging, release, labile, non-labile, sorption,
desorption, redox chemistry, kinetics, soils, sediments, sedimentary, coprecipitation,
phosphate, mineral phosphate species, cyanobacterial algae, planktonic algae, benthic
algae, sorption models, sorption mechanisms, sorption competition, nutrient cycling,
nutrient flux, nutrient loading, bottom water oxygen, organic matter, temperature, Fe-
bound, authigenic, anthropogenic, geogenic, and hypoxic. Additionally, boolean operators
(e.g. “and”, “or”, and “not”) were used with the above-mentioned keywords to adjust the
literature search. The literature search was limited by year, with publications spanning
between 1905 and 2023.3–5 However, special attention was paid to sentinel papers
published on P cycling in shallow lakes, particularly with respect to retention and release
of P in lakebed sediment. Particular attention was also given to recently published work
that is highly cited, which represents the state of the science for P cycling in environmental
systems, particularly Utah Lake and other shallow, eutrophic, alkaline lakes, where
applicable. Data was mined in this literature review to provide a summary of available P
retention, release, and speciation parameters for Utah Lake. The literature reviewed
herein can be found in an online library.
2 Phosphorus Cycling in Lakes
Although essential for life, P is considered a contaminant in water due its deleterious
effects on the environment at elevated concentrations.6,7 Elevated P in lakes decreases
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the water quality of the lake by favoring phytoplankton production which leads to
increased turbidity, cyanobacteria production, disappearance of submerged
macrophytes, shifts in fish communities typically toward non-native, less desirable
species, and diminished ability of zooplankton to control the phytoplankton.8 During times
of warm temperatures and adequate dissolved nutrients (notably N and P) in the water,
algal blooms can occur. Sometimes this algae photosynthesis in the epilimnion is paired
with cyanobacteria productivity and release of cyanotoxins into the water. These events
are referred to as harmful algal blooms (HABs). Harmful algal blooms have gained the
attention of the public and scientific community due to their impacts on fish, wildlife,
human health, and public perception.7 P is typically the limiting nutrient for HABs in
freshwater systems.

Prior to entering lakes, P can move through the environment in dissolved forms (e.g.
orthophosphate, HPO42-), or as particulates, providing essential nutrition for living
organisms. Phosphorus enters freshwater systems as rock formations weather and
release inorganic P or as biomass decomposes. It is then transported from upland
locations through overland, surface, or subsurface flow. As P migrates from its source,
some P is used and/or removed by physical, chemical, and biological processes,
particularly in wetlands.9 P inputs into lake systems, broadly stated, include surface and
groundwater and atmospheric deposition, and includes organic and inorganic, labile and
nonlabile, anthropogenic, biologic, and geogenic forms of P.8–12 This interconnected and
sinuous P cycling path makes it difficult to determine P provenance once it enters a lake.
However, understanding the P source can be important information for management and
regulation agencies.

Several factors influence retention of P in lakes. Lakebed sediments and the water column
are both significant as sources and sinks of P in shallow freshwater lakes.3,12–14
Phosphorus in the water column is either utilized for biologic productivity or will settle out
of the water column onto the sediment (see Section 3 of this document). In hard water
lakes with high mineral (e.g. calcite) content, the high concentrations of dissolved
minerals lead to considerable mineral precipitation and mineral-P coprecipitation from the
water column.

Lakebed sediments act as sinks for precipitates and other materials that drop out of the
water column. Fluxes exist where constituents move into the water column from the
lakebed or undergo diagenetic chemical reactions with sediment mineral surfaces,
microorganisms, and/or the porewater.15 The decomposition of deposited organic matter
drives biogenic reactions and subsequently impacts the pH and redox potential (Eh) of
the sediment, which conditions often differ significantly from the water column.16 In
addition to these biogeochemical processes, physical lakebed disturbance (wind
disturbance, wave action, bioturbation by bottom feeders, and boat wakes) occurs
regularly in shallow lakes such as Utah Lake and resuspends lakebed sediment,
potentially enhancing P exchange between sediment particles and the water column.17
These sedimentation, decomposition, and resuspension processes play important roles
in P cycling in shallow lakes. As P goes through its biogeochemical cycle, its form, or
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species, in sediment largely influences its fate – retention, release, or utilization – within
lakes (see Section 4 of this document).15

Shallow lakes are typically located in fertile basins adjacent to agriculture and dense
population.18 In addition to these anthropogenic stressors, shallow lakes are less able to
buffer increased nutrient inputs than deeper lakes, exacerbating additional nutrient
loading and potential for eutrophication.18 For these reasons, eutrophication in shallow
lakes is a complex biogeochemical process. Globally, several large shallow lakes are
plagued by eutrophication. This includes shallow lakes in North America: Champlain, Erie,
Okeechobee, Utah, Winnipeg), Europe: Lake Volkerak, Lough Neagh, Peipsi, Mälaren),
and China: (Taihu, Chaohu, Dianch).18 The frequency of water-sediment interactions
caused by resuspension in shallow lakes increases the influence of internal nutrient
loading and increased productivity.18 Despite degradation by anthropogenic forcing and
resultant eutrophication, these lakes are critical to their surrounding ecosystems,
including the biodiversity they support – including humans.

Utah Lake is a large, basin-bottom lake within Utah Valley adjacent to the Wasatch
Mountains at an elevation of 4489’ above sea level. It is on the eastern edge of the Basin
and Range in the western U.S. on the land of the indigenous Timpanogos Nation of the
Shoshone Tribe, Paiute, Goshute, and Ute peoples. The surface area of the lake is large
(~150 square miles), making it the 3rd largest freshwater lake in the western U.S. Despite
its large surface area, the lake is shallow (9’ avg., 18’ maximum depth) with a total water
volume of 902,000 acre-feet. The water inflow to the lake (930,000 ac-ft/year) comes from
tributaries and overland flow (79%), ground water (8%), and direct precipitation (13%).19
The water outflow from the lake goes to the Jordan River (32%) and a large fraction is
lost to evaporation (68%).19 Whereas these are the latest hydrologic numbers based
largely on hydrodynamic modeling20, other work has estimated a water balance for Utah
Lake using isotopes.21 According to this approach, the water inflow to the from tributaries
and overland flow totaled 22%, ground water totaled 72%, and direct precipitation totaled
6% and the 38% of the water outflow goes to the Jordan River, 19% of the outflow is
attributed to groundwater, and 43% is lost to evaporation.21 The water residence time of
Utah Lake is 0.42 water years, with 21% of the inflow stored in the lake.19,21The
evaporation rate in Utah Lake is roughly 5.53 mm/day (79.5 in/year), making Utah Lake
a restricted basin lake (>40% of the lake inflow evaporates).21 Its shallow nature and long
fetch create nearly continuous mixing of the water column and resuspension of lakebed
sediment.

In 2002, Utah Lake was listed as an impaired water body on Utah’s 303(d) list for elevated
total P (TP) levels. Utah Lake has most recently been assigned a 303(d) Category 5, “not
supporting”, designation by the Utah Division of Water Quality (DWQ) in 2022. There is
an active debate surrounding the relative amounts of P entering the lake from each P
source: tributaries, wastewater treatment plants, atmospheric deposition, and sediment.
Mass balance data indicate that Utah Lake sediments represent a net sink for nutrients
(namely P). It is estimated that 90% of external P loading to Utah Lake is retained within
the lake19,22, though the response of in-lake P concentrations to external P inputs suggest
this sink may be variable. Additional empirical data show that the sediments are active in
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terms of nutrient release.13 Studies have directly measured nutrient release in field flux
chambers and laboratory cores.12,23 Other studies have characterized P concentrations
across the lake.13,24,25 A recent master’s thesis investigated water column P chemistry
through the mixing of WWTP effluent with the lake.26

One probable mechanism for the P sink is calcite binding, as demonstrated in a recent
sediment core experiment by Goel et al. (2020). However, sediment-bound P exists in
different sediment fractions as well, including Fe oxides, which represents the potential
source of P release from sediment.12,13,27 In other words, although a large portion of the
P that enters Utah Lake is stabilized via complexation with calcite, some P undergoes
weaker complexation with other sediment constituents and thereby remains labile and
potentially mobilized. Although sediment-bound P fractions have been identified through
sequential chemical extractions, specific mineral forms have not been quantified. Further,
the reactions driving P binding, including magnitude and environmental drivers (e.g., pH,
P, cations), have not been fully described, nor have they been parameterized for modeling
the novel P cycling in Utah Lake.

3 Phosphorus Dynamics in the Water Column and Porewater of Shallow Lakes

3.1 Phosphorus Cycling in the Water Column
Phosphorus enters the water column in several different forms: dissolved inorganic P
(DIP, also commonly referred to as orthophosphate or soluble reactive P), dissolved
organic P (DOP), particulate inorganic P (PIP), or particulate organic P (POP, Fig. 1).10
Orthophosphate is the most bioavailable form of phosphate, and exists in different levels
of protonation (PO43-, HPO42-, or H2PO4-) depending on the pH of the water column (Fig.
2).10

Figure 1. Phosphorus cycling in shallow water, adapted from Reddy and Delaune (2008).
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Figure 2. Relative P speciation abundances based on pH values. Phosphate species
undergo sequential deprotonation (ionization) as pH increases, or protonation (ionization)
as pH decreases.
Phosphorus in the water column directly contributes to primary productivity and is
influenced by P loading levels, temperature, nutrient availability, pH, and redox potential.
Geochemical equilibria of species in natural waters and sediments are functions of the
solution composition, including the concentration of the element(s) of interest, as well as
the pH and Eh (or, pε). Applying the rules of thermodynamics and geochemical stabilities,
a Pourbaix diagram, or Eh-pH diagram, can be constructed to aid in predicting molecular
speciation in aqueous systems, such as Utah Lake (Fig. 3). Using these thermodynamic
predictions, it is expected that orthophosphate (HPO42-) is the dominant P species under
modern conditions of the Earth’s surface and therefore in the system in question: Utah
Lake. Phosphorus does occur in several oxidation states: phosphides (–3), diphosphides,
elemental P (0), hypophosphite (+1), phosphite (+3), and phosphate (+5), but phosphate
is the only commonly stable form of phosphate.10 The reduction of phosphate to phosphite
(PO33-) occurs only at very low redox potentials. In fact, no reduced oxidation state P is
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stable on the surface of the Earth, though they may occur under extreme conditions such
as hydrothermal vents or volcanism.28 The primary equilibrium constants that control the
ionization of phosphate ions are10:

In the water column, P can either be biologically utilized or settle out of the water column.
During algal blooms, pH increases as a result of the photosynthetic utilization of dissolved
CO2 from the water.29 Elevated pH levels can create a competitive advantage for
cyanobacteria, increasing the risk of HABs.30 This increase in pH can result in less P
availability due to abiotic removal of P from the water column via coprecipitation with
calcite. Conversely, calcite precipitation can buffer or decrease pH by producing CO2.31

3.2 Phosphorus Removal from the Water Column via Mineral Scavenging

The most common routes for P removal from the water column in most lake systems are
direct deposition onto the sediment or through biologic production. However, because
Utah Lake is saturated with respect to calcite, calcite precipitation in Utah Lake has been
estimated, using ion balances and the LKSIM model, at 100,000 to 200,000 tons/yr which
equates to a calcite sedimentation rate of 0.2 – 0.4 mm/yr.22,32 These numbers may need
to be revisited as the lake conditions under which these were determined occurred nearly
Figure 3. Thermodynamic Eh-pH stability diagram for phosphorus species
adapted from Pasek (2008).
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50 years ago (1975), in which time there has been considerable land use change and the
population has increased by 475% (144,000 in 1975 vs. 702,434 in 2022).33

Calcite precipitation is an important process in lakes, particularly those that are calcite-
rich. Dissolved Ca2+ ions precipitate as calcium carbonates with low solubility. Calcite
precipitation occurs in freshwater systems that are supersaturated with respect to calcite
that undergo an increase in pH, as occurs during photosynthetic activity spikes associated
with algal blooms and primary production. Calcite precipitation can also occur when CO2
is volatilized, or water temperature increases.34 The initial stage of calcite precipitation
requires a nucleation site, which then reduces the activation energy required for calcite
crystal formation. Calcite nucleation and subsequent precipitation can be initiated by
bacteria and algae.35,36 pH is an important factor when considering calcite precipitation,
as well as Ca2+ dissolution from calcite minerals. At pH 7 or below, Ca2+ dissolution is
common. Calcite’s ability to scavenge phosphate is maximized around pH 7.5.37 At pH 8
or above, calcite is stable and Ca2+ dissolution is negligible. At these elevated pH levels,
calcite precipitation and phosphate-calcite coprecipitation regularly occur via interface
coupled dissolution and precipitation.37

It is generally accepted that phosphate coprecipitates with calcite in freshwater systems.34
Calcite-phosphate coprecipitation happens as the calcite precipitate crystal grows and
interacts with inorganic P. These initial P-calcite reactions are surface sorption
phenomena, albeit poorly understood. The mechanisms of this P retention, or
scavenging, are complex and involve surface complexation, nucleation, and growth of
calcium phosphate precipitates on the surface of calcite.37 The particular retention
mechanism for a given system is dependent on P concentrations, ionic strength and
composition (e.g. which divalent cations are present and at what concentrations), and
pH.34,38 The retention mechanism thus dictates the molecular form of the calcite-
phosphate coprecipitate. For instance, at pH 8.0 it has been shown (using 31P NMR
spectra) that the dominant form of calcite-phosphate coprecipitate is type-B carbonated
hydroxyapatite in model calcite-phosphate systems.37 The rate kinetics of phosphate
sorption and calcite-phosphate coprecipitation are rapid and follow a bi-phasic pattern.
The initial reactions occur in less than 30 seconds, following by a slower step that takes
1-4 hours to reach equilibrium.39,40

Coprecipitation differs from sorption in that sorption is a surface phenomenon and
coprecipitation is the integration of P into a crystalline structure with calcite. It has been
hypothesized that sorption and nucleation occur simultaneously in these scenarios.41
Once adsorbed, the chemi-sorbed, surface-bound P is then occluded into the bulk calcite
structure as crystal growth continues.39 Conversely, the presence of inorganic P in
solution can partially or completely inhibit calcite crystal growth and, therefore, decreases
the efficacy of this natural P removal mechanism.42,43 In other words, increased P levels
lead to enhanced eutrophication and diminished ability of calcite to remove P through
coprecipitation.

Calcite precipitation may be inhibited by dissolved organic matter in addition to phosphate
concentrations.35,42 Phosphate can inhibit precipitation of calcite at high levels, and
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phosphate-inhibition of calcite has been recorded at levels as low as 2.5 ug P L-1.42,43 The
likely mechanism controlling this inhibition is the competition between phosphate (PO43-
), carbonate (CO32-), and bicarbonate (HCO3-) ions for calcite or Ca2+ sorption sites. This
phosphate-induced inhibition mechanism helps explain Utah Lake’s supersaturation with
respect to Ca2+.

Whereas many lakes experience episodic “whiting events” of large-scale calcite
precipitation, Utah Lake is seemingly perpetually experiencing large scale calcite
precipitation, as observed by its milky color, a constant visual reminder of Utah Lake’s
oversaturation with respect to calcite. This calcite over saturation originates with the
substantial amount of evaporation this restricted basin lake experiences.36

Using previous mass-balance based estimates of calcite precipitation in Utah Lake along
with the stoichiometric ratios of potential calcium phosphates, it is possible to estimate a
possible range of P scavenged from Utah Lake waters via calcite coprecipitation. This
has previously been estimated at a rate of 245 tons yr-1.22 A more sophisticated approach
to predicting coprecipitation has been proposed, using a general coprecipitation equation,
approximate coprecipitation equation, and/or a constant coprecipitation equation.34 The
general coprecipitation equation (assuming constant temperature) is defined as:

∆𝑛𝑃𝑇= 𝜎𝑁𝐴𝜕∫ℎ(𝑠𝑛𝑙)d𝑡
0 𝑛𝐶𝑎𝑇 ;

the approximate coprecipitation equation is defined as:

ℎ(𝑃𝑇,𝐶𝑎𝑇,𝑛𝐻)=[𝑃𝑇]𝐾14′(𝐾1𝛼+𝐾2)
{𝐾14′+[𝐶𝑎𝑇]+[𝑃𝑇]𝐾14′(𝐾1𝛼+𝐾2)};

and this approximate coprecipitation equation is reduced when h is assumed to be
constant following an assumption that the surface density of inorganic phosphate remains
constant during coprecipitation. This reduced equation is known as the constant
coprecipitation equation and is defined as:

𝑛𝑃𝑇= 𝜎𝑁𝐴𝜕ℎ𝑛𝐶𝑎𝑇 .

Variables listed in the above equations are defined as: h(sol) is a function used to
constrain coprecipitation based on solution chemistry; 𝑛𝐶𝑎𝑇 is the number of moles of
calcium containing species; 𝑛𝑃𝑇 is the number of moles of P containing species; 𝜕 is the
molecular surface area of calcite; 𝜎 is the maximum surface density of coprecipitated
phosphate; 𝐾1 and 𝐾2 are adsorption equilibrium constants for unprotonated and
monoprotonated phosphate, respectively; 𝑃𝑇 is the total P concentrations; and 𝐾14′ is the
apparent equilibrium constant for the complexation reaction between Ca2+ and HPO42-.
These models have not been applied to Utah Lake waters.

In addition to this theoretical approach, precipitation can be measured directly. Calcite
precipitation can be measured experimentally by observing Ca elimination from the water
when the system is near calcite saturation levels.44 This is more difficult in the field than
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the laboratory due to the dynamic nature of natural systems. In natural systems, the rate
of calcite precipitation can be determined by determining the calcite portion of the
sedimentation flux.35

In addition to calcite scavenging of P, iron and manganese can scavenge phosphate from
water bodies.45,46 In well-oxygenated waters, iron oxyhydroxides are dominant, though
measurable quantities of the reduced form, Fe2+, may exist. Utah Lake remains well
oxygenated due to its wind-induced mixing, thus creating oxidizing conditions in the water
column that favor the presence of colloidal or particulate iron oxyhydroxides (Fe3+) which
readily settle out of the water column. Most of the Fe entering lakes does so as
particulates.47 When Fe2+ oxidizes to Fe3+ in the water column, amorphous iron
hydroxides are formed (e.g. ferrihydrite or lepidocrosite). Iron oxides that are present in
the water column may be reactive or unreactive, depending on the environmental
conditions and form of the Fe oxide.48 The reactive forms are more likely to sorb
oxyanions such as phosphate, but they are also more likely to be reduced at the redox
boundary within the sediment. This reduction of iron hydroxides can lead to the release
of Fe-sorbed phosphate.

3.3 Sediment Pore Water
The sediment pore water, or interstitial water, serves as the main conduit between the
sediment and the water column. Although pore water typically contains less than 1% of
the total P found in the sediment, these P concentrations are typically greater than those
in the water column.8 Pore water P and water column P establish an equilibrium through
molecular diffusion. In addition to diffusion, groundwater can cause hydrostatic pressure
gradients that create upward flow of pore water across the sediment-water interface.

Utah Lake pore water data is sparse. Randall et al. (2019) collected bulk porewater
samples by centrifuging saturated sediments from the top 5 cm using an Ekman dredge.
These pore water results show total dissolved P concentrations average approximately
0.6% of the total P found in the sediment and an order of magnitude higher than water
column total dissolved P, with sediment pore water on the eastern portion of the lake
higher than that on the western portion.

Sediment pore water can be sampled by separating the water from the sediment via
centrifugation after collecting cores or bulk samples (like via Ekman dredge).13
Additionally, depth-resolved pore water can be sampled by installing equilibration dialysis
devices known as “peepers”–acrylic assemblies with distinct chambers filled with
deoxygenated, deionized water equipped with a semi-permeable membrane for
equilibration.49 Discrete depth pore water can be collected using piezometers along the
shore. To collect larger volumes of porewater with more flexibility in sample handling while
maintaining depth resolved pore water sampling, modified Hesslein peepers can be
used.50 Another common method is dilution and centrifugation of sections of an impact
core.51

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4 Phosphorus Retention and Release in Lakebed Sediments

Several factors influence P retention in shallow lakes including the hydrology (i.e. water
residence time, depth, mixing), biogeochemistry (water pH, conductivity, P and Ca2+
concentrations), sediment physiochemical properties, and redox conditions at the
sediment-water interface.52 This section focuses on the hydrobiogeochemical controls
on P in lakebed sediments and water column-sediment interactions.
4.1 Forms of Phosphorus in Lakebed Sediments
Phosphorus exists within lakebed sediments as mineral complexes (i.e. calcium,
aluminum, or iron), sorbed to mineral surfaces, dissolved porewater P, or as organic P or
bound to organic matter.53
4.1.1 Inorganic P
Calcium-bound (calcite-bound) P is a large portion of the total P found in sediments of
Utah Lake and similar alkaline lakes with marl sediments.3,4,12,13,52 Whereas some lakes
may contain a marl (CaCO3 rich sediment) layer within their sediment cores, there is a
continuous marl layer to a depth of at least 1m for much of Utah Lake, enhancing the
important role of this P binding mechanism in Utah Lake.

Another important form of inorganic P in sediment is that fraction bound to iron oxide and
hydroxide minerals. Under aerobic conditions, such as littoral sediments, surface wetland
sediments, or at the sediment-water interface of well-mixed aerobic shallow lakes,
inorganic P can be bound to Fe and take the form of ferric phosphate (FePO4) also
referred to as iron(III) phosphate, or as the mineral strengite.10 However, under reducing
conditions, the sediment experiences reductive dissolution of iron(III) oxides, resulting in
the release of Fe-bound P. Thus, the ability of Fe oxides to sorb P is contingent on the
redox conditions of the sediment.

Sequential extraction procedures are commonly used to determine the speciation of P in
sediments. These procedures typically use a sequence of chemical reagents with specific
reactions and increasing strength to determine how the P is bound in the sediment. The
initial one or two steps of P sequential extraction procedures (deionized water and sodium
bicarbonate extractions) are often considered to be the bioavailable fraction, or those
fractions that are loosely bound.8,54,55 Previous studies12,13 have speciated P in Utah Lake
sediments using sequential extraction, but used different sequential extraction methods.
Hogsett et al.12 found that on average most of the sediment P was in the Ca bound fraction
(65%) or the metal oxide (Fe/Mn) bound fraction (16%), whereas Randall et al.13 found
that on average most of the sediment P was in the metal oxide (Fe/Mn) bound fraction
(49%) or the Ca bound fraction (39%). Both studies reported low levels of loosely bound
P (4-7%).

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4.1.2 Organic P
Organic P can account for more than 40% of total P in soils and sediments. Organic forms
of P in sediments are complex, but can be lumped into easy decomposable P molecules
(nucleic acids, phospholipids, and sugar phosphates) and slowly decomposable P
molecules (inositol phosphates—phytin).9 In order for organic P to be utilized by
organisms, it must be broken down via hydroloysis. This process of breaking down
organic P to inorganic, bioavailable P is known as P mineralization. Phosphorus
mineralization in the sediment-water column is influenced by biological, chemical, and
physical environmental factors. Microbial mediation is a key aspect of organic P
mineralization. Microbes can breakdown P, but only if the substrate conditions (aerobic,
anaerobic) are favorable and if other nutrients and electron acceptors – O2 (aerobic), NO,
Fe3+, Mn4+ (facultative anaerobic) and SO2–4, CO2 (obligate anaerobic) – are present.56

Like inorganic P, extraction methods can also be used on the organic P pool.
Operationally defined fractions of organic P include: “(1) a labile pool, extracted with 0.5
M NaHCO3, (2) a moderately labile pool, consisting of acid soluble organic P and alkali
soluble inorganic P, (3) a moderately resistant fraction (fulvic acid P) and (4) a highly
resistant fraction (humic acid P and humin P)”.10

The limitation with the extraction methods for speciating both inorganic and organic P is
that they may oversimplify the complexity of P speciation by assigning operationally
defined “pools”, and only provide indirect evidence with no direct linkage to mineralogy.
Recent spectroscopic advances have enabled in-situ observation of organic P species
using nuclear magnetic resonance spectroscopy (31P-NMR) or P-Near Edge X-ray
Fluorescence Spectroscopy (P-NEXAFS). Direct observation of the P molecular
environment has the ability to differentiate between inorganic phases and organic phases,
as well as identify specific inorganic or organic species (apatite vs. strengite or
phosphonates vs. phosphates).57 However, obtaining time at a synchrotron facility to
perform the P-NEXAFS is competitive and may take months or years before time is
allocated to perform the analyses. phosphates).57

4.2 Phosphorus Retention in Sediments

Sediment retains P via several mechanisms including adsorption, absorption,
coprecipitation, and occlusion. Many of these mechanisms rely on the mineral fractions
of the sediment. Environmental parameters (e.g., pH, redox potential, temperature)
control when and to what extent P is retained by these different mechanisms.

4.2.1 Phosphorus retention by calcite

Phosphate sorption by calcite in shallow hardwater lakes is rapid and extensive.39,58 This
process can occur at the sediment-water interface and in the water column, and is
influenced by pH, ionic strength, chemical activity, and P loading in solution and in the
solid phase. Phosphorus sorption by calcite is typically less stable than Ca-P
13
coprecipitation.59 Some studies show that increased pH results in increased sorption,39
and others showing the opposite - decreased sorption with increased pH.58,60 These
varied results may be experimental design artifacts but are illustrative of the dynamic
interactions between P and calcite. As with most sorption phenomena, ionic strength
influences P sorption onto calcite: increased ionic strength results in decreased P sorption
onto calcite.43,58 Chemical activity also influences P sorption onto calcite: decreased CO32-
activity results in increased P sorption onto calcite.58

Sorption capacity for P on calcite has been reported in the 1-2 umol m-2 range, despite
the theoretical number of calcium surface sites being up to 8.3 umol m-2.58 This
discrepancy exists because these sites are usually not all occupied by phosphate and
calcite-P experiences heterogeneous complexation – bidentate, monodentate, and other
complexation methods. Additionally, carbonate sites on calcite can interact with divalent
cations such as Ca2+ and Mg2+, with the divalent cations acting as bridges to PO43- ions.61
This cation bridging can increase P sorption onto calcite. Both sorption and
coprecipitation (as discussed in 3.1) can be effective natural mechanisms of P removal
from shallow lakes.

4.2.2 Phosphorus retention by other minerals

Iron-P complexes and minerals (i.e. vivianite) can be common in lake sediments via
phosphate adsorption to Fe hydroxides. The OH group of iron hydroxides are commonly
the active site for PO43- adsorption.62

Although phosphate itself is not redox-active, its release from sediments can be impacted
by redox potential due to its association with redox-active minerals such as Fe
(hydr)oxides. Anaerobic conditions, or those conditions where the redox potential is
negative enough that oxygen is no longer the terminal electron acceptor, can induce
reductive dissolution of mineral oxides.8,9 This process will reduce ferric iron forms (Fe3+)
to ferrous iron forms (Fe2+), resulting in solubilization of the iron mineral and the release
of any elements, including P, that are sorbed to that iron (hydr)oxide or bound as an Fe-
P mineral phase such as strengite. The reductive dissolution of Fe-oxides can occur at
redox potential values as high as +100 mV, but commonly occurs at redox potential values
near 0 mV.63 This leads to the release of P bound to Fe minerals under reducing
conditions. The total Fe:P in surface sediments is negatively correlated to the release of
soluble reactive P. In other words, sediments with high Fe:P ratios are less likely to release
soluble reactive P than those with low Fe:P ratios, such as Utah Lake. The release of Fe-
bound P under reducing conditions and sorption of P by Fe under reducing conditions
creates a cycle of P retention and release that can occur on small spatial scales (< 1cm)
at or near the oxycline of a waterbody.47,48 For well oxygenated shallow lakes such as
Utah Lake, this is typically at or below the sediment surface.

Because Utah Lake is well-mixed and shallow, the water column likely remains oxic much
of the time. This working hypothesis was bolstered by the findings of Williams et al.
(2023).4 This study used trace metal ratios to infer depositional redox conditions in Utah
14
lake and determined the sediment depositional environment to be oxic on average.64
Algal-bloom induced hypoxia or anoxia may occur within the lake, but is likely short-lived
and local. While these results provide valuable insight into the depositional redox
conditions of the sediments within Utah Lake, no published data is available for measured
redox conditions in the sediments of Utah Lake. The companion report to this literature
review, therefore, collected redox potential measurements within the sediment of Utah
Lake, results forthcoming.65

In addition to Ca and Fe, aluminum (Al) can also complex with P in sediment. But Al-P
complexes differ from Fe-P complexes in that they are not redox sensitive. In fact,
aluminum hydroxide (alum, Al(OH)3) irreversibly sorbs P, resulting in the application of
alum (aluminum sulfate) in lakes and lake sediments for long-term improvements in lake
water quality. Adsorption of P to Al(OH)3 can be inhibited by ionic competition effects –
specifically silicate (at concentrations > 200 uM) and humic acid.66

As early as 50 years ago, researchers began investigating the mineralogic composition
of the sediment in Utah Lake.4,12,13,23,25,26,67,68 It is accepted that the lakebed is primarily
composed of marl sediments – calcium bearing minerals typically comprise > 60% of the
total sediment mass and approximately 40-80% of the total sediment P is bound in this
fraction.12,13 However, there has been some ambiguity related to other mineral fractions
within the lake and the relative abundance of P held by these mineral fractions. For
instance, Randall et al. reported higher relative amounts of P bound to redox sensitive
oxides than any other report or publication (> 40% of total P across 10 lakebed sediment
samples).13 Typically the P bound to oxides is between 15-25% of the total P.12,68 The
sediment mineral composition varies across the lake, as does the total P concentration
(Fig. 4).13,24,67 This large discrepancy in reported mineral oxide bound P in the sediment
makes it difficult to predict the potential for redox-related release of sediment bound P.
Therefore, it is important for additional work to be conducted to reach a consensus
regarding the mineral fraction of the sediment to which P is bound and, in turn, the
subsequent redox-mediated retention and release of P.

15
Figure 4. Utah Lake sediment phosphorus and mineral content. Figures were created
using an inverse distance weighting technique in the Spatial Analyst package of ArcGIS
Pro with data from Randall et al. (2019) and Sonerhelm et al. (1974).

4.2.3 Phosphorus retention and release in Utah Lake sediments

Previous work has attempted varying forms of sorption isotherm or mixing experiments
with Utah Lake sediments.26,69 Randall (2017) determined that Utah Lake sediments have
a “high” sorption capacity for P, based on sorption determined as a change
(disappearance) in the relative percent of initial P concentrations in solution.69 This study
also concluded that muddy or fine-grained sediments have higher P sorption capacity.
Taggart (2021) extrapolated from a series of sorption/desorption experiments that
coprecipitation is an important P retention mechanism in Utah Lake sediments, but no
express parameters were reported.26

16
These previous studies failed to parameterize P sorption in Utah Lake sediments.
Although they discussed sorption capacity, no sorption capacity was determined.
Similarly, batch sorption experiments were conducted but pH was not controlled. The
results were not modeled in a way that produced parameters such as partitioning
coefficients, sorption capacity, or sorption rate kinetics.

Sorption isotherms can be useful experiments for parameterizing sorption behavior.
Sorption experiments allow us to observe the effects of a single factor affecting P-sorption
in a system by keeping all other factors constant. Sorption isotherm experiments are
performed by mixing water and sediment until equilibrium and measuring the change in
aqueous P. When only a single variable is altered (e.g. P concentration) and all others are
controlled to remain the same, this data can be modeled to derive important parameters
such as total sorption, sorption capacity, partitioning coefficients, and equilibrium P
concentrations.

To determine the rate at which sorption and desorption are occurring, or the kinetics, a
different experimental approach must be applied. Typical kinetic rate experiments use a
flow cell to flow a solution through a reaction chamber or column at a known flow rate.
The effluent from the reaction chamber is then collected in known volumes and preserved
for analysis. Stirred-flow, miscible displacement, and column experiments are common
approaches for kinetic reaction rate experiments in sediments. The stirred-flow (SF)
method is particularly useful because the sorbent is exposed to a greater number of ions
than in a static batch system.70 Also, the flowing solution removes any desorbed/unsorbed
species, helping prevent secondary precipitation and quantify the advective flow of P
through the system. The stirred-flow (SF) method is particularly useful because the
sorbent is exposed to a greater number of ions than in a static batch system.70 Also, the
flowing solution removes any desorbed/unsorbed species, helping prevent secondary
precipitation and quantify the advective flow of P through the system. The enhanced
temporal resolution associated with SF is more representative of natural system
evolution.

The water levels in Utah Lake vary seasonally and year-to-year based on climatic
conditions and water management. These water level changes result in the drying and
rewetting of lakebed sediment, particularly in the littoral zone. Approximately 10-15% of
Utah Lake is Littoral.71 Cycling between dry and wet periods for these sediments alters
sediment properties such as redox conditions, which in turn alter P release, though recent
studies found that sediment PO4-P was not correlated with seasonal shifts related to
littoral sediment.71,72 Phosphorus is typically released during the rewetting cycle and the
amount of P release is a function of the sediment drying history, amount of drying, change
in sediment sorption capacity, and the concentration of P that is loosely bound in the
sediment.14,73–75 Phosphorus flux from Utah Lake sediments has been calculated to
average between -0.004 and 0.071.12 Although environmental factors (pH, DO) were
considered and monitored, no significant correlations were found between P flux and
those environmental conditions.

17
5 Conclusion
In conclusion, the status of P cycling in Utah Lake is largely controlled by the complex
interplay between P inputs, primary productivity, and P loading to the sediment,
porewater, and surface water. The aspects that control the P biogeochemical cycling
within Utah Lake include pH, redox conditions, calcite concentration (solid and
aqueous), calcite precipitation, Ca-P coprecipitation, mineral concentration (solid and
aqueous), mineral (particularly Fe/Mn) complexation with P, primary productivity,
resuspension events, and P speciation. These are all factors of sediment-water
interactions in Utah Lake and are paramount in P retention and release in Utah Lake.
Some questions remain to reach a consensus regarding the some of these factors
(particularly P speciation and redox conditions). Future work should conduct further P
speciation in the sediment in order to reach a consensus. Additionally, redox-targeted
sampling and measurement should be done to better understand the dynamics of
oxidation-reduction in Utah Lake and its sediment.

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