Phytoplankton may serve as a key entry for methylmercury (MeHg) into aquatic food webs however very few studies have quantified the bioconcentration of MeHg in marine phytoplankton from seawater, particularly for non-diatoms. Experiments using 203Hg to measure MeHg uptake rates and concentration factors in six marine phytoplankton species belonging to different algal classes were conducted and the influence of light, temperature, and nutrient conditions on MeHg bioaccumulation were determined. All algal species greatly concentrated MeHg out of seawater, with volume concentration factors (VCFs) ranging from 0.2 × 105 to 6.4 × 106. VCFs were directly related to cellular surface area-to-volume ratios. Most of the cellular MeHg was found in the cytoplasm. Temperature, light, and nutrient additions did not directly affect MeHg uptake in most species, with the exception that the dinoflagellate Prorocentrum minimum displayed significantly greater uptake per cell at 18°C than at 4°C, suggesting an active uptake for this species. Passive transport seemed to be the major pathway for most phytoplankton to acquire MeHg and was related to the surface area-to-volume ratio of algal cells. Environmental conditions that promoted cell growth resulted in more total MeHg associated with cells, but with lower concentrations per unit biomass due to biodilution. The very high bioconcentration of MeHg in marine phytoplankton is by far the largest bioconcentration step in marine food chains and variations in algal uptake may account for differences in the amount of MeHg that ultimately builds up in different marine ecosystems.

Tunas are apex predators in marine food webs that can accumulate mercury (Hg) to high concentrations and provide more Hg (~40%) to the U.S population than any other source. We measured Hg concentrations in 1292 Atlantic bluefin tuna (ABFT, Thunnus thynnus) captured in the Northwest Atlantic from 2004 to 2012. ABFT Hg concentrations and variability increased nonlinearly with length, weight, and age, ranging from 0.25 to 3.15 mg kg−1, and declined significantly at a rate of 0.018 ± 0.003 mg kg−1 per year or 19% over an 8-year period from the 1990s to the early 2000s. Notably, this decrease parallels comparably reduced anthropogenic Hg emission rates in North America and North Atlantic atmospheric Hg0 concentrations during this period, suggesting that recent efforts to decrease atmospheric Hg loading have rapidly propagated up marine food webs to a commercially important species. This is the first evidence to suggest that emission reduction efforts have resulted in lower Hg concentrations in large, long-lived fish.

Methylmercury (MeHg) is known to biomagnify in marine food chains, resulting in higher concentrations in upper trophic level animals than their prey. To better understand how marine copepods, an important intermediate between phytoplankton and forage fish at the bottom of the food chain, assimilate and release MeHg, we performed a series of laboratory experiments using the gamma-emitting radiotracer 203Hg2+ and Me203Hg with the calanoid copepod Acartia tonsa. Assimilation efficiencies (AEs) of Hg2+ and MeHg ranged from 25 to 31% and 58 to 79%, respectively, depending on algal diets. The AEs were positively related to the fraction of mercury in the cytoplasm of the algal cells that comprised their diet. Efflux rates of Hg2+ (0.29/d) and MeHg (0.21/d) following aqueous uptake were similar, but efflux rates following dietary uptake were significantly lower for MeHg (0.11-0.22 /d) than Hg2+ (0.47-0.66 /d). The calculated trophic transfer factors (TTFs) in copepods were >1 for MeHg and consistently low (≤0.2) for Hg2+. We used the parameters measured in this study to (1) quantitatively model the relative importance of MeHg sources (water or diet) for copepods, and to (2) predict the overall MeHg concentrations in copepods in different marine environments. In general, MeHg uptake from diet accounted for most of the body burden in copepods (>50%). For an algal diet whose MeHg dry weight bioconcentration factor (BCF) is ≥106, over 90% of a copepod's MeHg body burden can be shown to derive from diet. Our model-predicted MeHg concentrations in the copepods were comparable to independent measurements for copepods in coastal and open-ocean regions, implying our measured parameters and model are applicable to natural waters.

The largest bioconcentration step of most metals, including methylmercury (MeHg), in aquatic biota is from water to phytoplankton, but the extent to which dissolved organic matter (DOM) affects this process for MeHg largely remains unexplored in marine systems. This study investigated the influence of specific sulfur-containing organic compounds and naturally occurring DOM on the accumulation of MeHg in a marine diatom Thalassiosira pseudonana. Initial uptake rate constants and volume concentration factors (VCFs) of MeHg were calculated to evaluate MeHg enrichment in algal cells in the presence of a range of organic compound concentrations. At environmentally realistic and higher concentrations, the addition of glycine and methionine had no effect on algal MeHg uptake, but thiol-containing compounds such as cysteine and thioglycolic acid reduced MeHg accumulation in algal cells at high added concentrations (> 100 times higher than naturally occurring concentrations). However, environmentally realistic concentrations of glutathione, another thiol-containing compound as low as 10 nM, resulted in a decline of ~ 30% in VCFs, suggesting its possible importance in natural waters. Humic acid additions of 0.1 and 0.5 mg C/L also reduced MeHg VCFs by ~ 15% and ~ 25%, respectively. The bioaccumulation of MeHg for T. pseudonana in coastal waters with varying levels of dissolved organic carbon (DOC) was inversely correlated with bulk DOC concentrations. Generally, naturally occurring DOM, particularly certain thiol-containing compounds, can reduce MeHg uptake by phytoplankton.

Due to their recalcitrant nature and ubiquitous use, per-and polyfluoroalkyl substances (PFAS) will continue to be major water treatment hurdles. Although effective water treatment technologies exist for physical removal of many PFAS from water (e.g., activated carbon and ion-exchange resin), a PFAS-concentrated waste stream is generated as an end product that can potentially reintroduce PFAS back into the environment. Thus, there is an increased interest in developing destructive technologies to decompose and mineralize PFAS directly in water or in these waste streams. High energy electron beam (e-beam) accelerators have been used for water treatment to degrade a wide range of recalcitrant contaminants, including PFAS, since the 1960s. However, large-scale applications of e-beam for water treatment are restricted due to its high energy consumption and inability to treat large flow rates. Considering there are very few available technologies for destructive removal of PFAS, this study provides a critical review on the treatment of PFAS by direct irradiation of contaminated water by e-beam from an energy consumption point of view. To date, very limited studies have been conducted to investigate the success of this technology to treat PFAS. Results from the limited studies were not directly comparable due to the variation in operating conditions and water quality parameters used in the studies. Here, for the first time, we develop and apply the concept of electrical energy per order (EE/O) to assess the performance of e-beam for PFAS treatment. Results show that EE/O is a better performance parameter than the G value of e-beam for interstudy comparisons and to evaluate the effects of water quality and operating parameters on e-beam performance. We additionally developed a kinetic scheme to predict the performance of e-beam to treat PFAS and revealed that the competition between species to react with aqueous electrons is the determinant factor influencing PFAS degradation efficiency. Comparison of EE/O values of e-beam (range: 31−176 kWh m −3 order −1 ) with other destructive technologies (range: 5−9595 kWh m −3 order −1 ) suggest that e-beam, for PFAS treatment, is a promising approach under favorable conditions. This review further elucidates the feasibility and limitations of e-beam technology that could be improved upon to potentially make e-beam viable for large-scale water treatment applications.

Many environmentally relevant poly-/perfluoroalkyl substances (PFASs) including perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) exist in different isomeric (branched and linear) forms in the natural environment. The isomeric distribution of PFASs in the environment and source waters is largely controlled by the source of contamination and varying physicochemical properties imparted by their structural differences. For example, branched isomers of PFOS are relatively more reactive and less sorptive compared to the linear analogue. As a result, the removal of branched and linear PFASs during water treatment can vary, and thus the isomeric distribution in source waters can influence the overall efficiency of the treatment process. In this paper, we highlight the need to consider the isomeric distribution of PFASs in contaminated matrices while designing appropriate remediation strategies. We additionally summarize the known occurrence and variation in the physicochemical properties of PFAS isomers influencing their detection, fate, toxicokinetics, and treatment efficiency.

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Identifying prey resource pools supporting fish biomass can elucidate trophic pathways of pollutant bioaccumulation. We used multiple chemical tracers (carbon [δ13C] and nitrogen [δ15N] stable isotopes and total mercury [THg]) to identify trophic pathways and measure contaminant loading in upper trophic level fishes residing at a reef and open-ocean interface near Eleuthera in the Exuma Sound, The Bahamas. We focused predominantly on the trophic pathways of mercury bioaccumulation in dolphinfish Coryphaena hippurus and wahoo Acanthocybium solandri, 2 commonly consumed pelagic sportfish in the region. Despite residing within close proximity to productive and extensive coral reefs, both dolphinfish and wahoo relied almost exclusively on open-ocean prey over both short and long temporal durations. A larger isotopic niche of dolphinfish suggested a broader diet and some potential prey differentiation between the 2 species. THg concentrations in dolphinfish (0.2 ± 0.1 ppm) and wahoo (0.3 ± 0.3 ppm) were mostly below recommended guidelines for humans (US Environmental Protection Agency (EPA) = 0.3 ppm, US Food and Drug Administration (FDA)= 1.0 ppm) and were within ranges previously reported for these species. However, high THg concentrations were observed in muscle and liver tissue of commonly consumed reef-associated fishes, identifying a previously unrecognized route of potentially toxic Hg exposure for human consumers on Eleuthera and neighboring islands.