Determination of the specific surface area of snow using ozonation of 1,1-diphenylethylene

We measured the kinetics of ozonation reaction of 1,1-diphenylethylene (DPE) in artificial snow, produced by shock freezing of DPE aqueous solutions sprayed into liquid nitrogen. It was demonstrated that most of the reactant molecules are in direct (productive) contact with gaseous ozone, thus the technique produces snow with organic molecules largely ejected to the surface of snow grains. The kinetic data were used to evaluate the snow specific surface area (～70 cm(2) g(-1)). This number is a measure of the availability of the molecules on the surface for chemical reaction with gaseous species. The experimental results were consistent with the Langmuir-Hinshelwood type reaction mechanism. DPE represents environmentally relevant compounds such as alkenes which can react with atmospheric ozone, and are relatively abundant in natural snow. For typical atmospheric ozone concentrations in polar areas (20 ppbv), we estimated that half-life of DPE on the surface of snow grains is ～5 days at submonolayer coverages and -15 °C.     

Photochemical degradation of PCBs in snow

This work represents the first laboratory study known to the authors describing photochemical behavior of persistent organic pollutants in snow at environmentally relevant concentrations. The snow samples were prepared by shock freezing of the corresponding aqueous solutions in liquid nitrogen and were UV-irradiated in a photochemical cold chamber reactor at -25 degrees C, in which simultaneous monitoring of snow-air exchange processeswas also possible. The main photodegradation pathway of two model snow contaminants, PCB-7 and PCB-153 (c approximately 100 ng kg(-1)), was found to be reductive dehalogenation. Possible involvement of the water molecules of snow in this reaction has been excluded by performing the photolyses in D2O snow. Instead, trace amounts of volatile organic compounds have been proposed to be the major source of hydrogen atom in the reduction, and this hypothesis was confirmed by the experiments with deuterated organic cocontaminants, such as d6-ethanol or d8-tetrahydrofuran. It is argued that bimolecular photoreduction of PCBs was more efficient or feasible than any other phototransformations under the experimental conditions used, including the coupling reactions. The photodegradation of PCBs, however, competed with a desorption process responsible for the pollutant loss from the snow samples, especially in case of lower molecular-mass congeners. Organic compounds, apparently largely located or photoproduced on the surface of snow crystals, had a predisposition to be released to the air but, at the same time, to react with other species in the gas phase. It is concluded that physicochemical properties of the contaminants and trace co-contaminants, their location and local concentrations in the matrix, and the wavelength and intensity of radiation are the most important factors in the evaluation of organic contaminants' lifetime in snow. Based on the results, it has been estimated that the average lifetime of PCBs in surface snow, connected exclusively to the photoreductive dechlorination process, is 1-2 orders of magnitude longer than that in surface waters when subjected to the equivalent solar radiation. However, in case that the concentration of the hydrogen peroxide in natural snow is sufficient, the photoinduced oxidation process could succeed the photoreductive dechlorination and evaporative fluxes as the major sink.     

Simulating the influence of snow on the fate of organic compounds

Snow scavenging, a seasonal snowpack, and a dynamic water balance are incorporated in a non-steady-state generic multimedia fate model in order to investigate the effect of snow on the magnitude and temporal variability of organic contaminant concentrations in various environmental media. Efficient scavenging of large nonpolar organic vapors and particle-bound organic chemicals by snow can lead to reduced wintertime air concentrations and incorporation in the snowpack. The snow cover functions as a temporary storage reservoir that releases contaminants accumulating over the winter during a short melt period, resulting in temporarily elevated concentrations in air, water, and soil. The intensity of these peaks increases with the length of the snow accumulation period. Organic chemicals of sufficient volatility (log KOA < 9; e.g., light polychlorinated biphenyls) can volatilize from the snowpack, resulting in springtime concentration maxima in the atmosphere. The behavior of fairly water-soluble chemicals during snowmelt depends on their relative affinity for the newly formed liquid water phase and the rapidly diminishing ice surface-quantitatively expressed by their interface-water partition coefficient (KIW). Chemicals with a preference for the dissolved phase (low KIW; e.g., pentachlorophenol) can become enriched in the first meltwater fractions and experience a temporary concentration peak in lakes and rivers. Organic chemicals that are neither volatile enough to evaporate from the snowpack nor sufficiently water soluble to dissolve in the meltwater (e.g., polybrominated diphenyl ethers) sorb to the particles in the snowpack. These particles may be sufficiently contaminated to constitute the major input route to the terrestrial environment upon release during snowmelt. Because wintertime deposition to the snowpack may be higher than to a non-snow covered surface, this can result in higher soil concentrations of persistent organic contaminants in the long term. The potential ecotoxicological significance of peak exposures demands a better understanding of the role of snow in the fate of organic contaminants.     

Organochlorine pesticide and polychlorinated biphenyl concentrations in snow, snowmelt, and runoff at Bow Lake, Alberta

We present analyses of the concentrations of organochlorine (OC) contaminants (including organochlorine pesticides and PCBs) in snow, snowmelt, and runoff in glacier and snowmelt fed streams at Bow Lake, Alberta in two contrasting hydrological years (1997 and 1998). The study investigates the variability in OC burdens in snow across the catchment, the elution of OCs from the snowpack, and the relationship between OC concentrations in streams and the annual snowpack. Snowpacks in forested sites were thinner and had lower OC concentrations than snowpacks in open or sparsely vegetated sites. The first snowmelt samples exhibited very high contaminant concentrations relative to the snowpack, and even the more hydrophobic compounds (Dieldrin, DDTs, and PCBs) were highly concentrated in meltwater. Interannual changes in the mean OC concentrations in streams did not reflect year-to-year changes in the snowpack contaminant concentrations. The results indicate that the extent of glacial ice melt may be more important than mean snowpack burdens as a control on OC concentrations in runoff in glacial catchments.     

Rapid changes in PCB and OC pesticide concentrations in arctic snow

The short-term fate of polychlorinated biphenyl (PCB) and organochlorine (OC) pesticides in the surface snowpack was investigated by taking consecutive air and snow samples over a 12 day period at Troms? in the Norwegian Arctic. A wide range in PCB and OC pesticide concentrations was observed in snow and was attributed to the systematic decrease in concentrations that occurred over the study period. For example, sigmaPCB concentrations ranged from 2500 to 300 pg L(-1) (meltwater) with a rapid decrease observed during the first 96 h. Rates of decline (ks) conformed to first-order kinetics, with similar rates observed for all compounds measured in this study (k5 = 0.01 +/- 0.001 h(-1)). Because the particle bound fraction accounted for <10% of the individual PCB and OC burden in the snow, then the fraction lost may be accounted for by desorption, following notable increases in snow density (and presumably, decreases in snow surface area). The fraction of chemical present in the fresh snow (phis) was found to be exponentially related to changes in snow density (deltarho). Relatively small increases in p following snowfall result in a large loss of sorbed chemical, presumably due to decreases in snow surface area. Later sampling of the same snow layer, but buried under fresh snowfall, revealed a notable increase in both PCB and OC concentrations. This would indicate a possible downward migration of these chemicals from the fresh snow into deeper snow layers, suggesting that re-emission of desorbed chemical from the interstitial pore spaces to the overlying atmosphere may be complicated by this process.     

Oxidation of aromatic and aliphatic hydrocarbons by OH radicals photochemically generated from H2O2 in ice

Oxidation of aromatic and saturated aliphatic hydrocarbons (c = 10(-3)-10(-5) mol L(-1)) by the hydroxyl radicals, photochemically produced from hydrogen peroxide (c = 10(-1)-10(-5) mol L(-1)), in frozen aqueous solutions was investigated in the temperature range of -20 to -196 degrees C. While aromatic molecules (benzene, phenol, naphthalene, naphthalen-2-ol, or anthracene) underwent primarily addition-elimination reactions to form the corresponding hydroxy compounds, saturated hydrocarbons (cyclohexane, butane, methane) were oxidized to alcohols or carbonyl compounds via hydrogen abstraction and termination reactions. The results suggest that these photoreactions, taking place in a highly concentrated liquid or solidified layers covering the ice crystals, are qualitatively similar to those known to occur in liquid aqueous solutions; however, that probability of any bimolecular reaction in the environment ultimately depends on organic contaminant concentrations and oxidants availability at specific locations of the ice matrix, temperature, wavelength, and photon flux. They, moreover, support hypotheses that oxidation of organic impurities in the snowpack can produce volatile hydroxy and carbonyl compounds, which may consequently be released to the atmosphere.     

Organic contaminants in mountains

The study of organic contaminants at high altitudes is motivated by the potential risk that they pose to humans living in, or depending on resources derived from, mountains and to terrestrial and aquatic ecosystems in alpine areas. Mountains are also ideal settings to study contaminant transport and behavior along gradients of climate and surface cover. Information on organic contaminants in mountains is compiled from the literature and synthesized, with a focus on atmospheric transport and deposition, contaminant dynamics in alpine lakes and aquatic organisms, and concentration differences with altitude. Diurnal mountain winds, in connection with enhanced deposition at higher elevations caused by low temperatures and high precipitation rates, conspire to make mid-latitude mountains become convergence zones for selected persistent organic chemicals. In particular, the more volatile constituents of contaminant mixtures seem to become enriched, relative to the less volatile constituents at higher altitudes. For selected contaminants, concentration inversions (i.e., concentrations that increase with elevation) have been observed. A notable difference between cold trapping in high latitudes and high altitudes is the likely importance of precipitation. High rates of snow deposition in mid- and high-latitude mountains may lead to a large contaminant release during snowmelt. Regions above the tree line often have little capacity to retain the released contaminants, suggesting the potential for a highly dynamic contaminant fate situation during the snow-free season with significant revolatilization and runoff. The chemical and environmental factors that control the orographic cold trapping of organic contaminants should be examined further by measuring and comparatively interpreting concentration gradients along several mountain slopes with widely different characteristics. Future efforts should further focus on the bioaccumulation and potential effects of contaminants in the upper trophic levels of alpine food chains, on measuring more water-soluble, persistent organic contaminants, and on studying how climate change may affect contaminant dynamics in mountain settings.     

The role of mercury redox reactions in snow on snow-to-air mercury transfer

Wet deposition of Hg in snow represents a major air-to-land flux of Hg in temperate and polar environments. However, the chemical speciation of Hg in snow and its chemical and physical behavior after deposition are poorly understood. To investigate Hg dynamics in snow, we followed Hg0 and total Hg concentrations in a snowpack above a frozen lake over 1 month. Our results indicate that newly deposited Hg is highly labile in snowpacks. On average, Hg levels in particular snow episodes decrease by 54% within 24 h after deposition. We hypothesize that Hg depletion in snow could be caused by a rapid snow-to-air Hg transfer resulting from Hg(II) photoinduced reduction to volatile Hg0. Both snowmelt incubated under a UV lamp at 17 degrees C and solid snow incubated under the sun at -10 degrees C in clear reaction vessels yielded a statistically significant increase in Hg0(aq) with time of exposure, while the Hg0(aq) levels remained constant in the dark controls. The snow-to-air Hg transfer we observed in this study suggests that the massive Hg deposition events observed in springtime in northern environments may have less impact than previously anticipated, since once deposited, Hg could be rapidly reduced and re-emitted.     

Adsorption of phenanthrene on natural snow

The snowpack is a reservoir for semivolatile organic compounds (SVOCs) and, in particular, for persistent organic pollutants (POPs), which are sequestered in winter and released to the atmosphere or hydrosphere in the spring. Modeling these processes usually assumes that SVOCs are incorporated into the snowpack by adsorption to snow surfaces, but this has never been proven because the specific surface area (SSA) of snow has never been measured together with snow composition. Here we expose natural snow to phenanthrene vapors (one of the more volatile POPs) and measure for the first time both the SSA and the chemical composition of the snow. The results are consistent with an adsorption equilibrium. The measured Henry's law constant is H(Phen)(T) = 2.88 x 10(22) exp(-10660/7) Pa m2 mol(-1), with Tin Kelvin. The adsorption enthalpy is delta H(ads) = -89 +/- 18 kJ mol(-1). We also perform molecular dynamics calculations of phenanthrene adsorption to ice and obtain AHads = -85 +/- 8 kJ mol(-1), close to the experimental value. Results are applied to the adsorption of phenanthrene to the Arctic and subarctic snowpacks. The subarctic snowpack, with a low snow area index (SAI = 1000), is a negligible reservoir of phenanthrene, butthe colder Arctic snowpack, with SAI = 2500, sequesters most of the phenanthrene present in the (snow + boundary layer) system.     

The impact of particle-bound cadmium on bioavailability and bioaccumulation: A pragmatic approach

Studying the bioavailability of sediment-bound contaminants is complicated by many reasons, such as the variable composition of the particles, their temporal variations, the low levels of contaminant concentrations, their partitioning between diverse aqueous and particulate phases, and the variety of uptake routes that may involved with the biota. Therefore, simple and innovative methodologies should be tested as analogues for natural sediments. Among them, a diverse selection of artificial particles with well-defined surface properties, in the presence and absence of commercially available humic acids, has been proposed and used to investigate the bioavailability of several organic pollutants. For this work, this model was applied to investigate the uptake and accumulation of cadmium by the freshwater oligochaete Lumbriculus variegatus. The results showed that the uptake of the metal depended on the free dissolved Cd(II) species, while the contribution from the particles was negligible. Thus, the extent of cadmium bioaccumulated from each test system could be predicted as a function of the rate of absorption of the free dissolved Cd(II) species. These species were calculated either from the particle-water partition coefficients, or by using the MINEQL+ computer program. In general, the estimated accumulation levels were in good agreement with the experimental results.     

"Humic coverage index" as a determining factor governing strain-specific hydrocarbon availability to contaminant-degrading bacteria in soils

We report development of a novel parameter for quantifying the amount of humic and fulvic acids per unit surface area in a particular soil. This quantity, the "humic coverage index" (HCI), provides a measurement of the relative spatial extents and/or thicknesses of the humic/fulvic overlayers in different soils, and, therefore, can be used in modeling various soils' behavior in sequestration processes in which humic materials are involved. HCI is herein applied to modeling biodegradation of aromatic and aliphatic hydrocarbons (phenanthrene, pyrene, and hexadecane) by several bacterial strains. Results indicate that, for the cases studies here, contaminant biodegradation is highest at a particular HCI and decreases if the coverage density of humic material is lower or higher than this optimum value. The HCI value at which maximal degradation was observed varied across different strains (indicating strain-specific differences in ability to degrade contaminants sorbed to humic materials) and, to a lesser extent, across different contaminants. The HCI concept is also demonstrated to be useful in explaining soil-, strain-, and contaminant-specific variations in the ability of fulvic acid supplementation to enhance contaminant biodegradation. Finally, we show that, in general, strains which are comparatively better at degrading contaminants in high-HCI soils also show enhanced contaminant mineralization in vitro in the presence of humic acids, such as when hydrocarbons are adsorbed onto these materials.     

Rate of evolution of the specific surface area of surface snow layers

The snowpack can impact atmospheric chemistry by exchanging adsorbed or dissolved gases with the atmosphere. Modeling this impact requires the knowledge of the specific surface area (SSA) of snow and its variations with time. We have therefore measured the evolution of the SSA of eight recent surface snow layers in the Arctic and the French Alps, using CH4 adsorption at liquid nitrogen temperature (77 K). The SSA of fresh snow layers was found to decrease with time, from initial values in the range 613-1540 cm2/g to values as low as 257 cm2/g after 6 days. This is explained by snow metamorphism, which causes modifications in crystal shapes, here essentially crystal rounding and the disappearance of microstructures. A parametrization of the rate of SSA decrease is proposed. We fit the SSA decrease to an exponential law and find that the time constant alpha(exp) (day(-1)) depends on temperature according to alpha(exp) = 76.6 exp (-1708/7), with Tin kelvin. Our parametrization predicts that the SSA of a snow layer evolving at -40 degrees C will decrease by a factor of 2 after 14 days, while a similar decrease at -1 degrees C will only require 5 days. Wind was found to increase the rate of SSA decrease, but insufficient data did not allow a parametrization of this effect.     

Measuring the release of organic contaminants from melting snow under controlled conditions

The release of organic contaminants from a melting snowpack may result in temporary concentration peaks in receiving water bodies and respective pulse exposure of aquatic organisms. It is thus of considerable interest to gain a mechanistic and quantitative understanding of the processes determining the dynamic behavior of organic chemicals during snowmelt. Uniformly structured and contaminated snow was produced with the help of a newly designed snow gun and exposed to predetermined temperature conditions in a temperature-controlled cold room. The dry density and liquid water content during four freeze-thaw cycles was recorded continuously at different layers within the snowpack using time domain reflectometry, providing information on meltwater production and propagation as well as snow metamorphism. Fractionated meltwater samples were filtered and the dissolved and particle phase analyzed for five polycyclic aromatic hydrocarbons (PAHs) using gas chromatography/ mass spectrometry. The distribution of the PAHs between the dissolved and particulate fractions of the meltwater was strongly related to their hydrophobicity. Particle-bound PAHs were released late during the snowmelt, whereas PAHs in the dissolved phase were released uniformly during a two day melting period. Even though conductivity measurements indicated a preferential early elution of ions in the first meltwater fractions, no such "first flush" behavior was observed for soluble PAH. The developed laboratory-based approach opens up for the first time the possibility of reproducible experiments on organic contaminant behavior in snow. Future experiments will explore, in detail, how the properties of organic chemicals, the physical and chemical properties of the snowpack, and the temperature variations before and during the time of melting interact to determine the timing of chemical release from a snowpack.     

Changes in surface area and concentrations of semivolatile organic contaminants in aging snow

During the winter of 1999/2000 five snowpacks at Turkey Lake Watershed east of Lake Superior were sampled immediately after falling and again after several days of aging for the analysis of specific snow surface area and the concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The snow surface could be determined with a relative coefficient of variation of 6% using frontal chromatography, measuring the retention of ethyl acetate, a substance with known adsorption coefficient on the ice surface. The snow surface area of fresh snow varied from 1000 to 1330 cm2/g and was higher for snow falling during colder days. The aged snow samples had consistently lower surface areas ranging from 520 to 780 cm2/g, corresponding to an average loss of half of the initial surface area during aging. The rate of loss of surface area was faster at higher temperatures. Dieldrin, alpha-HCH, and gamma-HCH were the most abundant OCPs in snowmelt water, but endosulfan, chlordane-related substances, heptachlor epoxide, pp'-DDT, pp'-DDE, and chlorinated benzenes were also consistently present. Three midwinter snowpacks that aged during relatively cold temperatures generally experienced a loss of PCBs and OCPs that was of the same order of magnitude as the observed loss of snow surface area. However, no relationship between the extent of loss and the strength of a contaminants' sorption to snow was apparent. Few significant changes in snowpack concentrations of OCPs and PCBs were observed in a snowpack that fell at relatively high temperatures and aged under colder conditions. Concentrations of OCPs and PCBs increased in a late-winter snowpack that aged while temperatures rapidly increased to above freezing. Concentrations of pp'-DDE and endosulfan-II that increased in snowpacks that saw simultaneous decreases in the levels of pp'-DDT and endosulfan-I hint at the occurrence of sunlight induced conversions in snow. While surface area decreases clearly contribute to the loss of semivolatile organic compounds from metamorphosing snowpacks, other confounding factors play a role in determining concentration changes, in particular in wet snow.     

Influence of snow and ice crystal formation and accumulation on mercury deposition to the Arctic

Mercury is deposited to the Polar Regions during springtime atmospheric mercury depletion events (AMDEs) but the relationship between snow and ice crystal formation and mercury deposition is not well understood. The objective of this investigation was to determine if mercury concentrations were related to the type and formation of snow and ice crystals. On the basis of almost three hundred analyses of samples collected in the Alaskan Arctic, we suggestthat kinetic crystals growing from the vapor phase, including surface hoar, frost flowers, and diamond dust, yield mercury concentrations that are typically 2-10 times higher than that reported for snow deposited during AMDEs (approximately 80 ng/L). Our results show that the crystal type and formation affect the mercury concentration in any given snow sample far more than the AMDE activity prior to snow collection. We present a conceptual model of how snow grain processes including deposition, condensation, reemission, sublimation, and turbulent diffusive uptake influence mercury concentrations in snow and ice. These processes are time dependent and operate collectively to affect the retention and fate of mercury in the cryosphere. The model highlights the importance of the formation and postdeposition crystallographic history of snow or ice crystals in determining the fate and concentration of mercury in the cryosphere.     

Prediction of contaminant persistence in aqueous phase: a quantum chemical approach

At contaminated field sites where active remediation measures are not feasible, monitored natural attenuation is sometimes the only alternative for surface water or groundwater decontamination. However, due to slow degradation rates of some contaminants under natural conditions, attenuation processes and their performance assessment can take several years to decades to complete. Here, we apply quantum chemical calculations to predict contaminant persistence in the aqueous phase. For the test compound hexamethylphosphoramide (HMPA), P-N bond hydrolysis is the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. Through calculation of aqueous Gibbs free energies of activation for all potential reaction mechanisms, it is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. At pH 0, where the hydrolysis reaction is rapid enough to enable measurement, the experimentally determined rate constant and half-life are in excellent agreement with the predicted values. Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable.     

Phosphate imposed limitations on biological reduction and alteration of ferrihydrite

Biogeochemical transformation (inclusive of dissolution) of iron (hydr)oxides resulting from dissimilatory reduction has a pronounced impact on the fate and transport of nutrients and contaminants in subsurface environments. Despite the reactivity noted for pristine (unreacted) minerals, iron (hydr)oxides within native environments will likely have a different reactivity owing in part to changes in surface composition. Accordingly, here we explore the impact of surface modifications induced by phosphate adsorption on ferrihydrite reduction by Shewanella putrefaciens under static and advective flow conditions. Alterations in surface reactivity induced by phosphate changes the extent, decreasing Fe(Ill) reduction nearly linearly with increasing P surface coverage, and pathway of iron biomineralization. Magnetite is the most appreciable mineralization product while minor amounts of vivianite and green rust-like phases are formed in systems having high aqueous concentrations of phosphate, ferrous iron, and bicarbonate. Goethite and lepidocrocite, characteristic biomineralization products at low ferrous-iron concentrations, are inhibited in the presence of adsorbed phosphate. Thus, deviations in iron (hydr)oxide reactivity with changes in surface composition, such as those noted here for phosphate, need to be considered within natural environments.     

Mercury in the atmosphere, snow and melt water ponds in the North Atlantic Ocean during Arctic summer

Atmospheric mercury speciation measurements were performed during a 10 week Arctic summer expedition in the North Atlantic Ocean onboard the German research vessel RV Polarstern between June 15 and August 29, 2004. This expedition covered large areas of the North Atlantic and Arctic Oceans between latitudes 54 degrees N and 85 degrees N and longitudes 16 degrees W and 16 degrees E. Gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P) were measured during this study. In addition, total mercury in surface snow and meltwater ponds located on sea ice floes was measured. GEM showed a homogeneous distribution over the open North Atlantic Ocean (median 1.53 +/- 0.12 ng/m3), which is in contrast to the higher concentrations of GEM observed over sea ice (median 1.82 +/- 0.24 ng/m3). It is hypothesized that this results from either (re-) emission of mercury contained in snow and ice surfaces that was previously deposited during atmospheric mercury depletion events (AMDE) in the spring or evasion from the ocean due to increased reduction potential at high latitudes during Arctic summer. Measured concentrations of total mercury in surface snow and meltwater ponds were low (all samples <10 ng/L), indicating that marginal accumulation of mercury occurs in these environmental compartments. Results also reveal low concentrations of RGM and Hg-P without a significant diurnal variability. These results indicate that the production and deposition of these reactive mercury species do not significantly contribute to the atmospheric mercury cycle in the North Atlantic Ocean during the Arctic summer.     

Anaerobic transformation kinetics and mechanism of steroid estrogenic hormones in dairy lagoon water

Wastewater from concentrated animal feeding operations (CAFOs) frequently contains high concentrations of steroid estrogenic hormones. Release of these hormones into the environment may occur when CAFO wastewater is applied to agricultural lands as a nutrient and water source for crop production. To assess the potential risk of hormone contaminants derived from animal wastewater, we investigated the transformation kinetics and mechanisms of three natural estrogenic hormones (17α-estradiol, 17β-estradiol, and estrone) in aqueous solutions blended with dairy lagoon water under anaerobic conditions. Initial transformations of the three hormones in the dairy lagoon water were dominated by biodegradation and the degradation rates were temperature-dependent. The total amounts of hormones (initial concentration at 5 mg L(-1)) remaining in the solution after 52 days at 35 °C accounted for approximately 85%, 78%, and 77% of the initial amounts of 17α-estradiol, 17β-estradiol, and estrone, respectively. This observation suggests that these hormones are relatively stable over time and may accumulate in anaerobic or anoxic environments and anaerobic CAFO lagoons. A racemization reaction between 17α-estradiol and 17β-estradiol via estrone was observed in aqueous solutions in the presence of CAFO wastewater under anaerobic conditions. The initial hormone concentrations did not affect this degradation mechanism. A reversible reaction kinetic model was applied to fit the observed transformation dynamics. The degradation and regeneration of the parent hormone and its metabolites were successfully simulated by this model. The information in this study is useful for assessing the environmental risk of steroid hormones released from CAFO wastewater and to better understand why these hormone contaminants persist in many aquatic environments.