Determination of methylmercury in marine fish from coastal areas of Zhejiang,China

The concentration of methylmercury (MMC) and total mercury (TMC) in marine fishes (five species) frequently consumed in the coastal areas of Zhejiang province, China, was determined. The method of high-performance liquid chromatography–atomic fluorescence spectrometry (HPLC-AFS) with the microwave-assisted extraction was used for the MMC determination. TMC was analysed by a direct mercury analyser. MMC and TMC concentrations in five fish species ranged from 53 to 158?µg?kg^?1 and 60 to 172?µg?kg^?1, respectively. The proportion of MMC levels in TMC was greater than 80%. The highest MMC and TMC levels were found in Hairtail.     

Long-term selective retention of natural Cs and Rb by highly weathered coastal plain soils

Naturally occurring Cs and Rb are distinctly more abundant relative to K in the highly weathered upland soils of the Savannah River Site, South Carolina, than in average rock of Earth's upper continental crust (UCC), by factors of 10 and 4, respectively. Naturally occurring Cs has been selectively retained during soil evolution, and Rb to a lesser extent, while K has been leached away. In acid extracts of the soils, the Cs/K ratio is about 50 times and the Rb/K ratio about 15 times the corresponding ratios for the UCC, indicating that relatively large amounts of natural Cs and Rb have been sequestered in soil microenvironments that are highly selective for these elements relative to K. Cation exchange favoring Cs and Rb ions, and subsequent fixation of the ions, at sites in interlayer wedge zones within hydroxy-interlayered vermiculite particles may account for the observations. The amounts of stable Cs retained and the inferred duration of the soil evolution, many thousands of years, provide new insights regarding long-term stewardship of radiocesium in waste repositories and contaminated environments. Study of natural Cs in soil adds a long-term perspective on Cs transport in soils not available from studies of radiocesium.     

Acid-volatile sulfide oxidation in coastal flood plain drains: iron-sulfur cycling and effects on water quality

The effect of acid-volatile sulfide (AVS) oxidation on Fe-S cycling and water quality in coastal flood plain drains from acid-sulfate soil landscapes was examined using natural sediments and synthetic iron monosulfide. Oxidation of AVS occurred rapidly (half-time < or = 1 h) and produced elemental sulfur (S8(0)(s)) and iron oxyhydroxide (FeOOH(s)). The initial rapid AVS oxidation process occurred without significant acidification or changes to the aqueous-phase composition. Severe acidification (pH < 4) occurred only once S8(0)(s) began to oxidize to SO4 (within 2-3 days of the initial AVS oxidation). Our results demonstrate, for the first time with natural sediments, a significant pH-buffered (near-neutral) AVS oxidation step with the trigger to acidification being the oxidation of S8(0)(s). Acidification resulted in the pH-dependent release of large amounts of Al, Mn, Ni, and Zn even though the sediment metal content was low.     

Modeling of the solid-solution partitioning of heavy metals and arsenic in embanked flood plain soils of the rivers Rhine and Meuse

The aim of this study is to predict the solid-solution partitioning of heavy metals in river flood plain soils. We compared mechanistic geochemical modeling with a statistical approach. To characterize the heavy metal contamination of embanked river flood plain soils in The Netherlands, we collected 194 soil samples at 133 sites distributed in the Dutch part of the Rhine and Meuse river systems. We measured the total amounts of As, Cd, Cr, Cu, Ni, Pb, and Zn in the soil samples and the metal fraction extractable by 2.5 mM CaCl2. We found a strong correlation between heavy metal contamination and organic matter content, which was almost identical for both river systems. Speciation calculations by a fully parametrized model showed the strengths and weaknesses of the mechanistic approach. Cu and Cd concentrations were predicted within one log scale, whereas modeling of Zn and Pb needs adjustment of some model parameters. The statistical fitting approach produced better results but is limited with regard to the understanding it provides. The log RMSE for this approach varied between 0.2 and 0.32 for the different metals. The careful modeling of speciation and adsorption processes is a useful tool for the investigation and understanding of metal availability in river flood plain soils.     

Evaluating the potential efficacy of mercury total maximum daily loads on aqueous methylmercury levels in four coastal watersheds

Of the approximately 780 U.S. EPA approved mercury total maximum daily loads (TMDLs), most specify a reduction in total mercury (Hg(T)) loads to reduce methylmercury levels in fish tissue, assuming a 1:1 correspondence. However, mercury methylation is more complex, and therefore, proposed load reductions may not be adequate. Using multiple regression with microlevel and macrolevel variables, the potential efficacy of mercury TMDLs on decreasing aqueous methylmercury levels was investigated in four coastal watersheds: Mugu Lagoon (CA), San Francisco Bay Estuary, Long Island Sound, and south Florida. Hg(T) and methylmercury levels were positively correlated in all watersheds except in Long Island Sound, where spatial differences explained over 40% of the variability in methylmercury levels. A mercury TMDL would be least effective in Long Island Sound due to spatial heterogeneity but most effective in south Florida, where the ratio between aqueous Hg(T) and methylmercury levels was close to 1 and the 95% confidence interval was narrow, indicating a probable reduction in aqueous methylmercury levels if Hg(T) loads were reduced.     

Fluorescent whitening agents in Tokyo Bay and adjacent rivers: their application as anthropogenic molecular markers in coastal environments

Two kinds of stilbene-type fluorescent whitening agents (i.e., DSBP and DAS1), minor components of laundry detergents, were analyzed in surface waters of Tokyo Bay and adjacent rivers and in sewage effluents to examine their usefulness as molecular markers in the marine environment. Sensitive determination using HPLC (high performance liquid chromatography) with fluorescence detection with postcolumn UV radiator was employed. DSBP and DAS1 were found in Tokyo rivers at concentrations of a few microg/L and approximately 1 microg/L, respectively. DSBP and DAS1 were widely distributed in Tokyo Bay waters at concentrations in the range of 0.019-0.264 microg/L and 0.021-0.127 microg/L, respectively. Comparison of these concentrations with those in sewage effluents (DSBP: 8 microg/L and DAS1: 2.5 microg/L on average) yielded sewage dilutions in Tokyo Bay on the order of 10(2). FWAs-salinity diagram in the Tamagawa Estuary showed fairly conservative behaviors of the FWAs with approximately 20% and approximately 10% removal of DSBP and DAS1, respectively. This is thought to be caused by photodegradation. The persistent nature of FWAs and their widespread distribution in coastal environments demonstrates the utility of FWAs in tracing the behavior of water from rivers and sewage outfalls. The DSBP/DAS1 ratio showed a decreasing trend from sewage effluents, to rivers, to Tokyo Bay, indicating selective photodegradation of DSBP. The DSBP/DAS1 ratio is proposed as an index of the degree of photodegradation and residence time and freshness of water mass in coastal environments.     

Mercury and methylmercury bioaccessibility in swordfish

Concentrations of mercury (Hg) in swordfish (Xiphias gladius) present a food safety problem for many countries. This study analyses total Hg (t-Hg) concentrations in 27 samples of swordfish marketed in Spain in 2005 and in their bioaccessible fractions (soluble concentration in gastrointestinal medium), obtained after applying an in vitro digestion method. Methylmercury (MeHg) was also determined in the bioaccessible fractions. t-Hg concentrations in the samples were 0.41–2.11 mg kg^?1 wet weight, with a mean of 0.96 ± 0.47 mg kg^?1 wet weight. A total of 37% of the samples exceeded the Hg limit set by Spanish legislation (1.0 mg kg^?1 wet weight). Bioaccessible t-Hg concentrations were 0.17–1.72 mg kg^?1 wet weight (0.63 ± 0.4 mg kg^?1 wet weight), corresponding to 38–83% (64% ± 14%) of t-Hg. Bioaccessible MeHg concentrations, representing 94% of the bioaccessible t-Hg concentrations, were 0.16–1.53 mg kg^?1 wet weight, with a mean of 0.49 ± 0.32 mg kg^?1 wet weight. Children and adults who regularly consume this product in Spain have Hg and MeHg intakes that exceed the tolerable daily intake limits recommended by the Food and Agricultural Organization/World Health Organization (FAO/WHO) and US Environmental Protection Agency (USEPA). These results show the need for recommendations about swordfish consumption by population groups at risk in Spain.     

Photooxidation and its effects on the carboxyl content of dissolved organic matter in two coastal rivers in the southeastern United States

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.     

Comparison of the molecular mass and optical properties of colored dissolved organic material in two rivers and coastal waters by flow field-flow fractionation

Colored dissolved organic material (CDOM) is an important sunlight absorbing substance affecting the optical properties of natural waters. However, little is known about its structural and optical properties mainly due to its complex matrix and the limitation of the techniques available. A comparison of two southwestern Florida rivers [the Caloosahatchee River (CR) and the Shark River (SR)] was done in terms of molecular mass (MM) and diffusion coefficients (D). The novel technique Frit inlet/frit outlet-flow field-flow fractionation (FIFO-FIFFF) with absorbance and fluorescence detectors was used to determine these properties. The SR receives organic material from the Everglades. By contrast, the CR arises from Lake Okeechobee in central Florida, receiving anthropogenic inputs, farming runoff, and natural organics. Both rivers discharge to the Gulf of Mexico. Fluorescence identified, for both rivers, two different MM distributions in low salinity water samples: the first was centered at approximately 1.7 kDa (CR) and approximately 2 kDa (SR); the second centered at approximately 13 kDa for both rivers, which disappeared gradually in the river plumes to below detection limit in coastal waters. Absorbance detected only one MM distribution centered at approximately 2 kDa (CR) and 2.2-2.4 kDa (SR). Fluorescence in general peaked at a lower MM than absorbance, suggesting a different size distribution for fluorophores vs chromophores. A photochemical study showed that, after sunlight, irradiated freshwater samples have similar characteristics to more marine waters, including a shift in MM distribution of chromophores. The differences observed between the rivers in the optical characteristics, MM distributions, and D values suggest that the CDOM sources, physical, and photochemical degradation processes are different for these two rivers.     

Distribution and fluxes of total and methylmercury in Lake Superior

Despite the importance and size of Lake Superior, little is known regarding the biogeochemical cycling or distribution of mercury within its waters. We present the results from two research cruises on total Hg (HgT) and methylmercury (MeHg) distributions in aqueous and particulate phases, and in offshore sediments. Open waters of Lake Superior are similar in HgT content to Lakes Michigan and Ontario (sub-ng L(-1)), whereas MeHg was only 1% of HgT. Seasonality in aqueous HgT distribution was observed, most likely from tributary inputs during Spring snowmelt. Suspended particles were enriched in MeHg relative to water and surficial sediments, suggesting enhanced particle partitioning followed by demethylation in the water column and in surface sediments. Distribution coefficients for mercury in surficial sediments were lower than those in suspended material, likely due to remineralization. Preliminary estimates of mass balance indicate that air-water exchange processes such as evasion and wet deposition dominate the HgT budget, due to the basin's relatively small watershed area relative to lake area. In contrast, methylmercury cycling within Lake Superior is influenced more strongly by watershed sources, as well as by sedimentary sources and photodemethylation. The Hg cycle in Lake Superior is unique in that it is more similar in many aspects to that in marine systems than in small lakes, where management data for freshwaters typically originates.     

Photodecomposition of methylmercury in an Arctic Alaskan lake

Sunlight-induced decomposition of monomethylmercury (MMHg) reduces its availability for accumulation in aquatic food webs. We examined MMHg degradation in epilimnetic waters of Toolik Lake (68 degrees 38' N, 149 degrees 36' W) in arctic Alaska, a region illuminated by sunlight almost continuously during the summer. MMHg decomposition in surface water of Toolik Lake is exclusively abiotic and mediated by sunlight; comparable rates of MMHg decomposition were observed in filter-sterilized and unfiltered surface waters incubated under in situ sunlight and temperature conditions, and no MMHg was degraded in unfiltered aliquots incubated in the dark. Rates of photodecomposition are first order with respect to both MMHg concentration and the intensity of photosynthetically active radiation (PAR), except at the lake surface where rates of photochemical degradation are enhanced relative to PAR intensity and may be attributed to an additional influence of ultraviolet light. The estimated annual loss of MMHg to photodecomposition in Toolik Lake, though limited to a 100-d ice-free season, accounts for about 80% of the MMHg mobilized annually from in situ sedimentary production, the primary source in Toolik Lake. These results suggest that greater light attenuation in lacustrine surface waters, a potential result of increased loadings of dissolved organic matter due to continued warming in the Arctic, may result in less photodecomposition and subsequently greater availability of MMHg for bioaccumulation.     

Total and methylmercury residues in tuna-fish from the Mediterranean sea

This study was carried out to determine the current levels of total mercury and methylmercury in the muscle tissue of albacore (Thunnus alalunga) and bluefin tuna (Thunnus thynnus) caught in the Mediterranean sea with the purpose of ascertaining whether the concentrations exceeded the maximum level fixed by the European Commission Decision. Total mercury concentrations ranged from 0.84 to 1.45 mg kg^-1 w.w. (av. 1.17 mg kg^-1 w.w.) and from 0.16 to 2.59 mg kg^-1 (av. 1.18 mg kg^-1 w.w.) in the muscle of albacore and bluefin tuna, respectively. In 78.6% of albacore and in 61.1% of bluefin tuna analysed, total mercury concentrations exceeded the maximum level fixed by the European Commission Decision (Hg = 1 µg g^-1 wet wt). In the two species, mercury was present almost completely in the methylated form, with percentages between 77 and 100% (av. 91.3%) in albacore and between 75 and 100% (av. 91%) in bluefin-tuna. In order to assess the potential health impact, the estimated weekly intake was calculated. The estimated weekly intake was far above the established Provisional Tolerable Weekly Intake for both species.     

Total mercury and methylmercury in Chinese rice and dietary exposure assessment

ABSTRACT

Total mercury levels and methylmercury levels were investigated for various grain parts (whole rice, rice husk, brown rice, polished rice, and bran) of 507 rice samples from 15 main rice-producing areas of China. The average total mercury contents in brown rice samples and polished rice samples were 4.2 and 3.3 μg/kg, respectively, the percentages exceeding the national standard limit were 0.59% and 0.39%, respectively. The average methylmercury levels were 2.9 and 2.4 μg/kg in brown rice and polished rice, respectively. The order of total mercury contents in different parts of rice was bran > brown rice > whole rice > rice husk > polished rice, and the order for methylmercury was bran > brown rice > whole rice > polished rice > rice husk. Total mercury intakes and methylmercury intakes were estimated for the Chinese population and the associated health risks were assessed.     

Legacy and fate of mercury and methylmercury in the Florida Everglades

Mass inventories of total Hg (THg) and methylmercury (MeHg) and mass budgets of Hg newly deposited during the 2005 dry and wet seasons were constructed for the Everglades. As a sink for Hg, the Everglades has accumulated 914, 1138, 4931, and 7602 kg of legacy THg in its 4 management units, namely Water Conservation Area (WCA) 1, 2, 3, and the Everglades National Park (ENP), respectively, with most Hg being stored in soil. The current annual Hg inputs account only for 1-2% of the legacy Hg. Mercury transport across management units during a season amounts to 1% or less of Hg storage, except for WCA 2 where inflow inputs can contribute 4% of total MeHg storage. Mass budget suggests distinct spatiality for cycling of seasonally deposited Hg, with significantly lower THg fluxes entering water and floc in ENP than in the WCAs. Floc in WCAs can retain a considerable fraction (around 16%) of MeHg produced from the newly deposited Hg during the wet season. This work is important for evaluating the magnitude of legacy Hg contamination and for predicting the fate of new Hg in the Everglades, and provides a methodological example for large-scale studies on Hg cycling in wetlands.     

Episodes of elevated methylmercury concentrations in prairie streams

Methylmercury (MeHg) and total mercury (THg) concentrations were determined weekly from late March through mid-December 2000 in unfiltered water samples from two prairie streams in south-central Minnesota. The Little Cobb River and County Ditch 86 drain predominantly agricultural watersheds, but riparian areas along much of the Little Cobb River are forested, whereas County Ditch 86 is a utilitarian drainage waterway with grassed riparian areas. Episodes of elevated MeHg concentration (1.3 ng/L) were observed in both streams in early May during a period of algal bloom. Between late May and late September, MeHg concentrations varied between 0.05 and 0.39 ng/L in the Little Cobb River and between 0.03 and 0.29 ng/L in County Ditch 86. Precipitation was well below average in August and September, and discharge in both streams ceased by late September. MeHg concentrations in the Little Cobb River increased dramatically in early October after autumnal leaf fall, increasing from 0.44 to 4.90 ng/L over a 5-week period. In contrast, MeHg concentrations in County Ditch 86 varied between 0.22 and 0.48 ng/L over the same time frame. The observed differences are thoughtto reflect differences in the amounts of litterfall entering the two streams. These results show that algal bloom and leaf fall events can result in elevated MeHg concentrations in surface waters, potentially leading to increased MeHg accumulation in fish.     

Uptake and elimination routes of inorganic mercury and methylmercury in Daphnia magna

Mercury (Hg) is an important environmental pollutant due to its highly toxic nature and widespread occurrence in aquatic systems. The biokinetics of Hg in zooplankton have been largely ignored in previous studies. This study examines the assimilation, dissolved uptake, and efflux of inorganic mercury [Hg(II)] and methylmercury (MeHg) in a freshwater cladoceran, Daphnia magna, and models the exposure pathways of Hg(II) and MeHg in the daphnids. The assimilation efficiencies (AEs) of both Hg species decreased significantly with increasing algal carbon concentrations. The dissolved uptake of Hg(II) and MeHg was proportional to the ambient concentration (ranging from environmentally realistic to high concentration over a 3-4 orders of magnitude variation), whereas MeHg had a slightly higher uptake rate constant (0.46 L g(-1) h(-1)) than Hg(II) (0.35 L g(-1) h(-1)). Surprisingly, the efflux rate constants of Hg(ll) and MeHg were rather comparable (0.041 -0.063 day(-1)). The release of both Hg(II) and MeHg via different routes (excretion, egestion, molting, and neonate production) was further examined at different food concentrations. It was found that regeneration into the dissolved phase was important for D. magna to eliminate both Hg species, but maternal transfer of Hg(II) (11-15%) and MeHg (32-41%) to neonates represented another important pathway for the elimination of Hg(II) and MeHg from the mothers. Modeling results suggest that food is an important source for MeHg exposure (47-98%), but water exposure represents 31-96% of Hg(II) accumulation in D. magna, depending on the variation of Hg bioconcentration factor in ingested food. Furthermore, MeHg predominates the bioaccumulation of Hg in D. magna even though MeHg constitutes only a small percentage of the total Hg in the water. The results strongly indicate that maternal transfer of Hg(II) and MeHg in freshwater zooplankton should be considered in manytoxicity testings and risk assessment in aquatic food chains.     

Research Watch: Phosphorus in rivers

Water.     

Evidence for elevated production of methylmercury in salt marshes

Depth variations of total mercury (Hg) and methylmercury (MeHg) concentrations were obtained in cores from nonvegetated sediments, sediments colonized by Sarcocornia fruticosa, Halimione portulacoides, and Spartina maritima and below-ground biomass in three Portuguese estuaries. Similar analyses were also performed on the above-ground plant tissues. Concentrations in below-ground biomass exceeded up to 9 (Hg) and 44 (MeHg) times the levels in sediments. Mercury and MeHg in below-ground biomass were up to 400 (Hg) and 4700 (MeHg) times higher than those found in above-ground parts, indicating a weak upward translocation. Methylmercury in colonized sediments reached 18% of the total Hg, which was 70 times above the maximum values found in nonvegetated sediments. Concentrations of MeHg in vegetated sediments were not related to plant type but were linearly proportional to the total mercury levels. The analysis of below-ground biomass at high depth resolution (2 cm) provided evidence that Hg and MeHg were elevated. The higher enrichment factors were found where the shifting of redox conditions suggested high microbial activity. Mercury and MeHg in below-ground tissues were a function of total levels in sediments and again were not plant-specific. These results suggest that the bioremediation of mercury-contaminated sediments is likely to increase the formation of methylmercury.