Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

Thermographic laser Doppler velocimetry using the phase-shifted luminescence of BAM:Eu2+ phosphor particles for thermometry.

Simultaneous point measurements of gas velocity and temperature were recently demonstrated using thermographic phosphors as tracer particles. There, continuous wave (CW) excitation was used and the spectral shift of the luminescence was detected with a two-colour intensity ratio method to determine the gas temperature. The conventional laser Doppler velocimetry (LDV) technique was employed for velocimetry. In this paper, an alternative approach to the gas temperature measurements is presented, which is instead based on the temperature-dependence of the luminescence lifetime. The phase-shift between the luminescence signal and time-modulated excitation light is evaluated for single BaMgAl10O17:Eu2+ phosphor particles as they cross the probe volume. Luminescence lifetimes evaluated in the time domain and frequency domain indicate that in these experiments, interferences from in-phase signals such as stray excitation laser light are negligible. The dependence of the phase-shift on flow temperature is characterised. In the temperature sensitive range above 700 K, precise gas temperature measurements can be obtained (8.6 K at 840 K) with this approach.

Dietary Accumulation of Inorganic Selenium by a Larval Amphibian (Hyla chrysoscelis) and Influence on Accumulation of Background Mercury.

Larval gray tree frogs (Hyla chrysoscelis) were exposed to inorganic Se (SeO2) added to the diet (10.2 and 86.3 ug/g dw) and monitored for accumulation and effect. Background concentrations of Hg were also measured in food and carcasses to assess possible effects of Se on Hg accumulation. Selenium was accumulated in a dose dependent manner, and life stages did not differ. No effects of Se exposure were observed on survival, growth, or time to metamorphosis. Mercury concentrations in carcasses, resulting from background concentrations in food, were significantly affected by the presence of Se. In the high Se treatment, Hg concentrations were significantly decreased relative to those in the low Se treatment and the control. Our study suggests that exposure to inorganic Se as SeO2 at the concentrations tested do not elicit adverse biological effects, but exposure to relatively high concentrations of Se may reduce accumulation of Hg from food.

Thermographic laser Doppler velocimetry.

We propose a point measurement technique for simultaneous gas temperature and velocity measurement based on thermographic phosphor particles dispersed in the fluid. The flow velocity is determined from the frequency of light scattered by BaMgAl10O17:Eu2+ phosphor particles traversing the fringes like in conventional laser Doppler velocimetry. Flow temperatures are derived using a two-color ratio method applied to the phosphorescence from the same particles. This combined diagnostic technique is demonstrated with a temperature precision of 4%-10% in a heated air jet during steady operation for flow temperatures up to 624 K. The technique provides correlated vector-scalar data at high spatial and temporal resolution.

Bromination of Marine Dissolved Organic Matter following Full Scale Electrochemical Ballast Water Disinfection.

An extensively diverse array of brominated disinfection byproducts (DBPs) were generated following electrochemical disinfection of natural coastal/estuarine water, which is one of the main treatment methods currently under consideration for ballast water treatment. Ultra-high-resolution mass spectrometry revealed 462 distinct brominated DBPs at a relative abundance in the mass spectra of more than 1%. A brominated DBP with a relative abundance of almost 22% was identified as 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, which is an analogue to several previously described 2,2,4-trihalo-5-hydroxy-4-cyclopentene-1,3-diones in drinking water. Several other brominated molecular formulas matched those of other known brominated DBPs, such as dibromomethane, which could be generated by decarboxylation of dibromoacetic acid during ionization, dibromophenol, dibromopropanoic acid, dibromobutanoic acid, bromohydroxybenzoic acid, bromophenylacetic acid, bromooxopentenoic acid, and dibromopentenedioic acid. Via comparison to previously described chlorine-containing analogues, bromophenylacetic acid, dibromooxopentenoic acid, and dibromopentenedioic acid were also identified. A novel compound at a 4% relative abundance was identified as tribromoethenesulfonate. This compound has not been previously described as a DBP, and its core structure of tribromoethene has been demonstrated to show toxicological implications. Here we show that electrochemical disinfection, suggested as a candidate for successful ballast water treatment, caused considerable production of some previously characterized DBPs in addition to novel brominated DBPs, although several hundred compounds remain structurally uncharacterized. Our results clearly demonstrate that electrochemical and potentially direct chlorination of ballast water in estuarine and marine systems should be approached with caution and the concentrations, fate, and toxicity of DBP need to be further characterized.

Tracing maternal transfer of methylmercury in the sheepshead minnow (Cyprinodon variegatus) with an enriched mercury stable isotope.

Maternal transfer of methylmercury (MeHg) to eggs is an important exposure pathway for developing offspring. However, our understanding of this process is limited, particularly in estuarine fish. We conducted a 91-day chronic laboratory exposure of Cyprinodon variegatus to four concentrations of dietary MeHg ranging from 0.04 to 9.90 µg g(-1) dw. Juvenile fish were fed a preoogenesis MeHg diet for 28 days, after which the diet was switched to a diet enriched with Me(199)Hg, spanning the period of oogenesis, allowing us to differentiate between mercury stored in female tissues and mercury assimilated from the maternal diet during oogenesis. We found that both maternal body burden and clutch size were strong predictors of egg Hg content. A constant percentage of preoogenesis Hg was transferred to eggs in each treatment. Additionally, preoogenesis Hg and during-oogenesis Hg were transferred proportionally to eggs, suggesting that both female tissues and the maternal diet during oogenesis are significant sources of Hg.

Fate and transport of ambient mercury and applied mercury isotope in terrestrial upland soils: insights from the METAALICUS watershed.

The fate of mercury (Hg) deposited on forested upland soils depends on a wide array of biogeochemical and hydrological processes occurring in the soil landscape. In this study, Hg in soil, soilwater, and streamwater were measured across a forested upland subcatchment of the METAALICUS watershed in northwestern Ontario, Canada, where a stable Hg isotope (spike Hg) was applied to distinguish newly deposited Hg from Hg already resident in the watershed (ambient Hg). In total, we were able to account for 45% of the total mass of spike Hg applied to the subcatchment during the entire loading phase of the experiment, with approximately 22% of the total mass applied now residing in the top 15 cm of the mineral soil layer. Decreasing spike Hg/ambient Hg ratios with depth in the soil and soilwater suggest that spike Hg is less mobile than ambient Hg over shorter time scales. However, the transport of spike Hg into the mineral soil layer is enhanced in depressional areas where water table fluctuation is more extreme. While we expect that this pool of Hg is now effectively sequestered in the mineral horizon, future disturbance of the soil profile could remobilize this stored Hg in runoff.

Differential patterns of accumulation and retention of dietary trace elements associated with coal ash during larval development and metamorphosis of an amphibian.

We performed an experiment in which larval gray tree frogs (Hyla chrysoscelis) were raised through metamorphosis on diets increased with a suite of elements associated with coal combustion residues (silver [Ag], arsenic [As], cadmium [Cd], chromium [Cr], copper [Cu], mercury [Hg], lead [Pb], selenium [Se], vanadium [V], and zinc [Zn]) at "low" and "high" concentrations. We quantified accumulation of metals at three life stages (mid-larval development, initiation of metamorphosis, and completion of metamorphosis) as well as effects on survival, metabolic rate, size at metamorphosis, and duration and loss of weight during metamorphosis. Most elements were accumulated in a dose-dependent pattern by some or all life stages, although this was not the case for Hg. For most elements, larval body burdens exceeded those of later life stages in some or all treatments (control, low, or high). However for Se, As, and Hg, body burdens in control and low concentrations were increased in later compared with earlier life stages. A lack of dose-dependent accumulation of Hg suggests that the presence of high concentrations of other elements (possibly Se) either inhibited accumulation or increased depuration of Hg. The duration of metamorphosis (forelimb emergence through tail resorption) was lengthened in individuals exposed to the highest concentrations of elements, but there were no other statistically significant biological effects. This study shows that patterns of accumulation and possibly depuration of metals and trace elements are complex in animals possessing complex life cycles. Further study is required to determine specific interactions affecting these patterns, in particular which elements may be responsible for affecting accumulation or retention of Hg when organisms are exposed to complex mixtures of elements.

Barriers and enablers in doping, anti-doping, and clean sport: A qualitative meta-synthesis informed by the theoretical domains framework and COM-B model.

To protect the integrity of sport, and the health of athletes, global anti-doping programmes seek to prevent doping, and elicit anti-doping and clean sport behaviours, through education, deterrence, detection, enforcement, and rules. To guide programme development, this meta-synthesis of qualitative research applied a behavioural science framework to identify barriers and enablers to doping, anti-doping, and clean sport. A systematic search of electronic databases up to May 2022, followed by critical appraisal, resulted in 73 included articles. Fifty-two articles reported the athlete perspective, thirteen included athletes, athlete support personnel (ASP), and other experts, and eight focused on ASP only. Rigorous methods of thematic synthesis were drawn upon to construct analytical themes in line with the theoretical domains framework (TDF) and the capability, opportunity, and motivation model of behaviour (COM-B). A wide range of barriers and enablers were identified which influenced capability, opportunity, and motivation to participate in a clean sport environment. The weight of evidence pointed to limitations in the current anti-doping education system in providing athletes and ASP with the knowledge and skills to protect against doping, as well as the significant influence of social and cultural norms in shaping doping and clean sport behaviours through a shared social identity, and risky contexts leading to moments of vulnerability to doping. We identified a need for anti-doping programmes to move beyond the current focus on athlete capability, and address the opportunity and motivation components of clean sport behaviours through a targeted and tailored focus on education, training, persuasion, modelling and environmental restructuring interventions.

Dietary selenomethionine exposure induces physical malformations and decreases growth and survival to metamorphosis in an amphibian (Hyla chrysoscelis).

Selenium (Se) is an essential micronutrient with a narrow therapeutic concentration range. The relative toxicity of Se increases as it is biotransformed into organic compounds, primarily selenomethionine (SeMet), within the aquatic food chain. Effects of aquatic Se contamination are well quantified for many freshwater fish and aquatic bird species, but impacts on amphibians are not well known. This study investigated the responses of larval Cope's gray tree frogs (Hyla chrysoscelis) fed a diet enriched with one of two concentrations of SeMet (50.1 and 489.9 µg Se g(-1) dw [low and high groups, respectively]) by way of a food-limited (ration) or ad libitum (ad lib) feeding regimen. The high dose caused 100 % mortality during the larval period independent of resource provision levels. Regardless of feeding regimen, the low dose decreased larval survival and successful metamorphosis relative to control treatments. The low dose also induced rear limb deformities in ≤73 % of individuals initiating metamorphosis. Providing low-dose food by way of a rationed feeding regimen decreased observed toxicity, likely because of decreased dietary exposure to SeMet relative to the low ad lib treatment. Individuals from the low ration treatment had decreased wet mass at initiation and completion of metamorphic climax (Gosner stages 42 through 46) compared with those from the control ad lib treatment, indicating that resource limitation combined with Se exposure might negatively affect energy stores after metamorphosis. However, lipid content analyses of recently metamorphosed individuals did not reveal any influence of treatment or resource provision on energy stored as lipids. The mean tissue Se concentration of individuals that received the low dose and completed metamorphosis was significantly greater than that of control ad lib or ration individuals at the same developmental stage. This study demonstrates that larval exposure to dietary SeMet can decrease growth and survival and induce deformities in a developing amphibian. Furthermore, retention of Se body burdens through metamorphosis suggests that surviving individuals can transport Se accumulated from contaminated aquatic environments into terrestrial food webs.

Context matters: athletes' perception of dopers' values, actions and vulnerabilities.

Background: Although athletes seem to hold uniform views towards non-dopers, their perception of dopers is more nuanced, reflecting positive and negative attributes. Research also indicates that rarely a single factor can explain doping, but a host of reasons that intertwine. A holistic understanding of how values play a role in decisions in anti-doping and the elements that influence athletes' doping vulnerability is timely and warranted. Methods: We recruited elite athletes from 13 countries representing 27 sports at a national or international level (N = 60) to participate as part of a larger research project. Data were collected via focus group interviews focusing on values, value priorities and perceptions about the role of values in doping as a phenomenon and in dopers' actions. Data were analysed using iterative thematic analysis. Results: Three themes were identified: (1) athletes' personal stance on doping, (2) dopers in the eyes of the anti-doping-compliant athletes, and (3) doping vulnerability is a balance. Athletes in this study strongly opposed doping but showed empathy and understanding toward athletes who doped under certain circumstances. Furthermore, athletes believed that "clean" and "doping" athletes are not always distinguished by the values they hold, leading to the realisation that all athletes can be vulnerable to doping at some point. This vulnerability is a balance between risks and protective factors in a complex interaction between environmental, personal, and situational influences. Each element (e.g., values, environment) can be a motivator or a barrier. Consequently, doping vulnerability is highly idiosyncratic and dynamic. Conclusion: If doping is not due to a lack of moral values but the consequences of combined risk factors that override the guiding function of values, then doping can happen to anyone, "good" athletes included. Developers and facilitators of anti-doping education programmes are advised to embrace this important aspect. The results also contribute to developing the doping vulnerability concept as a balance between risks and protective factors and draw attention to the clean athlete vulnerability, which is rooted in the combination of strategic performance enhancement via non-prohibited means, their exposure to anti-doping requirements and the constant high level of suspicion that surrounds them.

Simultaneous temperature, mixture fraction and velocity imaging in turbulent flows using thermographic phosphor tracer particles.

This paper presents an optical diagnostic technique based on seeded thermographic phosphor particles, which allows the simultaneous two-dimensional measurement of gas temperature, velocity and mixture fraction in turbulent flows. The particle Mie scattering signal is recorded to determine the velocity using a conventional PIV approach and the phosphorescence emission is detected to determine the tracer temperature using a two-color method. Theoretical models presented in this work show that the temperature of small tracer particles matches the gas temperature. In addition, by seeding phosphorescent particles to one stream and non-luminescent particles to the other stream, the mixture fraction can also be determined using the phosphorescence emission intensity after conditioning for temperature. The experimental technique is described in detail and a suitable phosphor is identified based on spectroscopic investigations. The joint diagnostics are demonstrated by simultaneously measuring temperature, velocity and mixture fraction in a turbulent jet heated up to 700 K. Correlated single shots are presented with a precision of 2 to 5% and an accuracy of 2%.

Food web restructuring across an urban estuarine gradient.

Food webs in urban estuaries support valuable ecosystem services that are subject to a wide range of stressors that can degrade the structure of trophic networks. Multiple trophic pathways stabilize food webs by providing complementary diet resources for consumers but the consequences of urbanization on estuarine food webs are relatively unknown. In estuarine creeks across an urban-to-suburban gradient, we demonstrate trophic decoupling of benthic and pelagic pathways, trophic niche contraction, and increasing human health risk arising with the same factors that are associated with ecological degradation. This suggests an urban estuarine paradox-human activities often create larger volumes of deep water habitat, yet human activities also render much of this area unproductive with measurable opportunity costs to food webs. Our findings emphasize the shared consequences of environmental degradation for the ecological integrity of urban estuaries and the health of urban communities that rely on estuaries for sustenance.

Differential patterns of accumulation and depuration of dietary selenium and vanadium during metamorphosis in the Gray Treefrog (Hyla versicolor).

Selenium (Se) and vanadium (V) are contaminants commonly found in aquatic systems affected by wastes derived from fossil fuels. To examine their effects on a widely distributed species of amphibian, we exposed gray tree frogs (Hyla versicolor) to Se (as SeO2) or V (as NaVO3) in their diet from the early larval period to metamorphosis. Concentrations of Se in Se-enriched food were 1.0 (Se control), 7.5 (Se low), and 32.7 (Se high) µg/g dw. Concentrations of V in V-enriched food were 3.0 (V control), 132.1 (V low), and 485.7 (V high) µg/g dw. Although we observed bioaccumulation of both metals throughout the larval period, no effects on growth, survival, metabolic rate, or lipid content were observed. Se concentrations in tissues did not vary among life stages, neither in Se low nor Se high treatments, such that maximum accumulation had occurred by the mid-larval period. In addition, there was no evidence of depuration of Se in either the Se low or the Se high treatments during metamorphosis. A strikingly different pattern of accumulation and depuration occurred in V-exposed individuals. In treatments V low and V high, maximum body burdens occurred in "premetamorphs" (i.e., animals with developed forelimbs but in which tail resorption had not begun), whereas body burdens in animals having completed metamorphosis were much lower and similar to those in larvae. These results suggest that compared with Se-exposed animals, V-exposed animals were able to depurate a substantial amount of accumulated V during the metamorphic period. In an ecologic context, it appears that amphibians exposed to Se during the larval period may serve as a vector of the metal to terrestrial predators, yet potential transfer of accumulated V to predators would largely be restricted to the aquatic habitat.

Combined fluorescent measurements, parallel factor analysis and GC-mass spectrometry in evaluating the photodegradation of PAHS in freshwater systems.

To better understand the transformation and photochemical fate of PAHs in aquatic environments, a custom-designed closed-circuit recirculation photodegradation system, combined with inline semi-continuous fluorescence and absorbance measurements, as well as modelling of excitation-emission (EEM) measurements with parallel factor analysis (PARAFAC), and GC-MS analysis, were combined to create a robust tool for holistically assessing the photodegradation of individual PAHs, their mixtures and photoproduct formation. Selected compounds included in the US EPA priority list, representing 2- to 6-ring compounds, were monitored individually and in mixtures, during 24 h photodegradation experiments. Experiments were conducted in solutions simulating ideal (ultrapure water) and environmentally relevant conditions (1.00 mg L-1 Suwannee River Natural Organic Matter (SRNOM)). The fluorescence, primary PARAFAC components and quantification data obtained by GC-MS, indicated that the decline in parent molecule concentration occurred rapidly within 200 min. The degradation rates of parent PAHs increased with aromaticity (6-ring ≫ 2-ring PAHs) and followed pseudo-first order degradation kinetics. The presence and transformation of degradation products, were captured by PARAFAC. NOM influenced the diversity of photoproducts. From the GC-MS results, photoproducts were only detected in Ant, BAnt and the PAH mixture solutions, but optical property analyses indicated that diverse changes occurred with all PAHs. Spectrometric and chromatographic data demonstrated that parent PAHs and photoproducts co-existed at various stages, which is significant for freshwater systems contaminated with these compounds if photoproducts have higher-toxic potential. These results may be used to model the hazard-potential associated with PAHs present in freshwater systems and understanding the mechanisms that govern their environmental fate.

Acute toxicity of the UV filter oxybenzone to the coral Galaxea fascicularis.

Coral reefs are impacted by a variety of anthropogenic stressors including inputs of chemical contaminants. Although data is currently limited, sunscreens containing ultraviolet (UV) filters have recently been suggested as an emerging class of chemical contaminants. To provide further data on the toxicity of the UV filter oxybenzone (benzophenone-3 or BP-3) to corals, we conducted three independent acute toxicity tests exposing the colonial stony coral Galaxea fascicularis to BP-3 (0.31 to 10 mg/L nominal concentrations). Assessments included daily analytical verification of the exposure concentrations, calculation of the lethal concentration to result in 50% mortality (LC50) and numerous biological endpoints to further investigate the potential impact to both the coral and symbiont. LC50s for the three tests were similar and averaged 6.53 ± 0.47 mg/L nominal concentration BP-3 (4.45 mg/L measured dissolved BP-3). BP-3 did not initiate coral bleaching or show a significant loss of symbionts from the coral tissue in this species as reductions in measurements used for bleaching (i.e. visual color, color saturation and photosynthetic pigment concentrations) were only seen concurrently with tissue loss (i.e. at ≥2.5 mg/L nominal concentration BP-3). Polyp retraction, the most sensitive endpoint of this test, was seen to be a sub-lethal behavioral response to BP-3 exposure. Using the calculated LC50 with measured concentrations from a high-quality UV filter monitoring study in Hawaii, a preliminary, conservative risk quotient for BP-3 was calculated at 0.032. These results suggest that BP-3 likely does not pose an acute risk of mortality to G. fascicularis and additional testing is required to determine sublethal impacts of BP-3 under environmentally relevant concentrations and longer-term chronic exposures. This study highlights complications in conducting toxicity tests with organic UV filters including under-estimations of exposure concentrations and provides recommendations to improve these methods for better comparisons between studies.

A Critical Review of Organic Ultraviolet Filter Exposure, Hazard, and Risk to Corals.

There has been a rapid increase in public, political, and scientific interest regarding the impact of organic ultraviolet (UV) filters to coral reefs. Such filters are found in sunscreens and other consumer products and enter the aquatic environment via direct (i.e., recreational activities, effluents) or indirect (i.e., land runoff) pathways. This review summarizes the current state of the science regarding the concentration of organic UV filters in seawater and sediment near coral reef ecosystems and in coral tissues, toxicological data from early and adult life stages of coral species, and preliminary environmental risk characterizations. Up to 14 different organic UV filters in seawater near coral reefs have been reported across 12 studies, with the majority of concentrations in the nanograms per liter range. Nine papers report toxicological findings from no response to a variety of biological effects occurring in the micrograms per liter to milligrams per liter range, in part given the wide variations in experimental design and coral species and/or life stage used. This review presents key findings; scientific data gaps; flaws in assumptions, practice, and inference; and a number of recommendations for future studies to assess the environmental risk of organic UV filters to coral reef ecosystems. Environ Toxicol Chem 2021;40:967-988. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Occurrence and distribution of UV-filters and other anthropogenic contaminants in coastal surface water, sediment, and coral tissue from Hawaii.

The occurrence of UV-filters in the environment has raised concerns over potentially adverse impacts on corals. In this study, the concentrations of 13 UV-filters and 11 hormones were measured in surface seawater, sediment, and coral tissue from 19 sites in Oahu, Hawaii. At least eight UV-filters were detected in seawater, sediment, and coral tissue and total mass concentrations of all UV-filters were <750 ng L-1, <70 ng g-1 dry weight (dw), and <995 ng g-1 dw, respectively. Four UV-filters were detected in water, sediment, and coral tissue at detection frequencies of 63-100%, 56-91%, and 82-100%, respectively. These UV-filter concentrations generally varied as follows: water, homosalate (HMS) > octisalate (OS) > benzophenone-3 (BP-3, also known as oxybenzone) > octocrylene (OC); sediment, HMS > OS > OC > BP-3; coral, OS ≈ HMS > OC ≈ BP-3. BP-3 concentrations in surface seawater were <10 ng L-1 at 12 of 19 sites and highest at Waikiki beach (e.g., 10.9-136 ng L-1). While BP-3 levels were minimal in sediment (e.g., <1 ng g-1 dw at 18 of 19 sites), and ranged from 6.6 to 241 ng g-1 dw in coral tissue. No quantifiable levels of 2-ethylhexyl 4-methoxycinnamate (also known as octinoxate) were recorded in surface seawater or coral tissues, but 5-12.7 ng g-1 dw was measured for sediment at 5 of 19 sites. No hormones were detected in seawater or sediment, but 17α-ethinylestradiol was present in three corals from Kaneohe Bay. Surfactant degradation products were present in seawater, especially at Waikiki beach. These results demonstrate ubiquitous parts-per-trillion concentrations of UV-filters in surface seawater and is the first report of UV-filters in coral tissue from U.S.A. coastal waters. These data inform the range of environmentally-relevant concentrations for future risk assessments on the potential impacts of UV-filters on coral reefs in Oahu, Hawaii.

Author Correction: Sulfate Reduction in Sediments Produces High Levels of Chromophoric Dissolved Organic Matter.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.