Determination of Organic Mercury in Biota, Plants and Contaminated Sediments Using a Thermal Atomic Absorption Spectrometry Technique

A simple, rapid procedure for the determination of organic mercury in sediments, plants and fish tissues has been developed and validated. Extraction and separation of organic mercury compounds from the sample matrix was achieved by an established procedure based on an acid leaching of the sample (H₂SO₄/KBr/CuSO₄), followed by extraction of the organic mercury halide with toluene and back-extraction with an aqueous solution of thiosulphate. Detection and quantification of mercury, in the liquid extracts, was made by atomic absorption spectrometry (AAS), following thermal decomposition of the sample. The method was evaluated using Certified Reference Material (CRM) BCR 463 (tuna fish), BCR 580 (estuarine sediment), IAEA-140TM (sea plant homogenate) and NRCC TORT-2 (lobster hepathopancreas). The recovery factors for organic mercury in all tested CRM were between 81–107%. The precision of the method has relative standard deviations of less than 10% for sediments and fish tissues and of less than 16% for plant material. The method was successfully applied to natural samples of sediments, plants, macroalgae and fish tissues collected from an estuarine ecosystem and could, therefore, be used for routine analyses.     

北江沉积物汞污染现状与评价初步研究

为了了解北江沉积物中汞污染现状、来源并评价其污染程度,在北江流域共采集19个沉积物样,用原子吸收法（AAS）和冷原子荧光法（CVAFS）分别测定了其总汞（THg）和甲基汞（MeHg）含量,比较了甲基化率,并用污染指数法对测定结果进行了评价。结果表明,北江沉积物THg含量为73.7～3 517 ng·g^-1（干重）,均值为607.6 ng·g^-1,MeHg含量为 0.392～2.384 ng·g^-1,均值为1.302 ng·g^-1,韶关冶炼厂为重要污染点源。各采样点甲基化率差异较大,进一步研究影响甲基化的因素具有重要意义。沉积物中THg、MeHg平均污染指数分别为3.04、26.04,表明均为中度污染。     

The methylmercury to total mercury ratio in selected marine,freshwater, and terrestrial organisms

Total and methylmercury concentrations were determined in muscle and organ tissue from a wide variety of marine and terrestrial organisms spanning several trophic levels. Sediment and water samples from many of the tissue sampling sites were also analyzed to assess the degree of mercury contamination to which the animals were exposed. The methylmercury to total mercury ratios were examined to determine whether this ratio is indicative of elevated exposure to organic or inorganic mercury and how it varies relative to tissue type and position in the food chain. As an ancillary study, a subset of these tissues was analyzed as 1) wet tissue, and 2) freeze-dried, ball-milled tissue to determine whether the form of sample preparation can adversely affect mercury analysis. Results indicate that the methylmercury to total mercury ratios generally approach unity only in muscle tissue of higher food chain carnivorous fish residing in waters that are relatively uncontaminated with respect to inorganic mercury species. Herbivorous terrestrial mammals and low food chain marine organisms tend to have very low methylmercury to total mercury ratios. Marine animals placed higher on the food chain, such as crabs and lobsters, exhibit somewhat higher methylmercury to total mercury ratios and can exhibit a large variation in this ratio between, organ tissue and muscle tissue of the same animal. The samples analyzed as both wet and freeze-dried, ball-milled tissue indicate that freezedrying and ball-milling in no way result in mercury loss or contamination and, in fact, result in better replicate analyses and create a sample sufficiently stable to be archived for several years without refrigeration.     

Influence of Natural Sources on Mercury in Water, Sediment and Aquatic Biota in Seven Tributary Streams of the East Fork of the Upper Carson River, California

The East Fork of the Upper Carson River (EFUCR) drainagebasin contains the Leviathan mine site, a known source of acidmine drainage, and numerous small prospects and mineralizedareas, some of which are enriched in mercury. In 1999 aninvestigation was undertaken to characterize total mercuryconcentrations in water, sediment, and whole aquaticmacroinvertebrates from seven tributaries of the EFUCR watershedon a seasonal time step. In the fall, methyl mercury in water,sediment and Stoneflys was determined for three sites. Both total and dissolved mercury in water at all sites, notimpacted by acid mine drainage, exhibited a seasonal trend withthe lowest concentrations occurring in the winter, higherconcentrations in the summer, and the highest concentrationsrecorded in the fall. Winter samples were taken during a periodof ice melt. It is hypothesized that the high fall concentrations were due to elevated mercury concentrations ingroundwater, which was recharging the stream under baseflow conditions and had interacted with substrate naturally enrichedin mercury. Mercury concentrations in Leviathan Creek wereelevated when acid mine drainage was being discharged directlyinto the Creek. Mercury concentrations in individual stoneflyscollected from specific stream reaches were similar, and methylmercury and total mercury concentrations in macroinvertebratetissue were roughly equivalent. Comparison of mercury bodyburden of macroinvertebrates between tributaries showed thatmacroinvertebrates in the Cottonwood Creek watershed had highermercury concentrations relative to the other sites. Thistributary had higher sediment mercury concentrations than allsimilar tributaries not impacted by acid mine drainage.     

Methylmercury in hair samples from different riverine groups,Amazon, Brazil

The present study was aimed to evaluate comparatively the levels of methylmercury (MeHg) in human hair, collected from different groups of Amazonian populations exposed to contamined fish. The study was undertaken in fishing villages and gold mining areas, mainly in the Tapajós and Madeira river basins, two of the main tributaries of Amazon river. The study population included 125 hair samples, chosen from a collection of over one thousand samples collected in different periods. Hair analyses were conducted with a new efficient extraction technique and measured with ECD-gas chromatographer. This analytical method presented good accuracy and precision when compared with standard hair samples from IAEA. A highly significant correlation was found at the interlaboratory exercise between National Institute for Minamata Disease and our laboratory at Federal University of Rio de Janeiro. The results of the present study showed, through hair analysis, a relationship between environmental contamination by mercury and methylmercury and dietary habits of the Amazon population. The highest levels of MeHg in hair samples were found in riverine population from upper Tapajós river and in riverine population from some tributaries of Madeira river, followed by population of fishing villages from Madeira river. Majority of the women of child-bearing age presented high MeHg concentration in hair samples (10 mg.kg-1). On the other hand, Yanomami Indians presented MeHg concentration below the limit tolerable of 6 mg.kg-1.     

Mercury in Small Freshwater Lakes: A Case Study: Lake Velenje, Slovenia

Lake Velenje is located in one of the most polluted regions ofSlovenia, the ?alek Valley. The major source of pollution is the coal-fired thermal power plant in ?o?tanj (?TPP). In the past, dumping of coal ash directly into Lake Velenje and drainage water from the ash disposal site resulted in unique chemical characteristics of the lake water, such as very high pH (10–12) and high concentrations of heavy metals. The introduction of a closed cycle ash transport system in 1995resulted in a very fast recovery of the lake water quality. The aim of our study was to establish the sources, fate and distribution of mercury in Lake Velenje. In order to establishrecent sources of mercury, total mercury and methylmercury concentrations were measured in various environmental samples(lake inflows, outflow, rainwater, sediments, etc.). Total mercury and methylmercury concentrations were measured at thesurface and at different depths to establish mercury cycling, its transport and chemical transformations in the lake. Generalwater quality parameters (such as pH, Eh, O₂, temperature,TDS, conductivity) were also determined. The results show that the major sources of mercury in Lake Velenje are lake inflows and wet deposition. Total mercury andmethylmercury concentrations in the water column are very low (total mercury: 0.2–2.7 ng L^-1; methylmercury: 20–86 pg L^-1) and can be compared to other non-contaminated freshwater lakes. These results suggest that the major form of mercury emitted from thermal power plant stacks is volatile Hg⁰, whichhas no or very little influence on the nearby surroundings, but rather is subject to long-range atmospheric transport.     

Influence of Physical and Chemical Characteristics on Mercury in Aquatic Sediments

Given the variation observed in mercury in fish from natural lakes, it is difficult to determine what represents a background mercury level. Mercury in aquatic sediments is a potential source of this trace metal to biota, notably fish. Site specific factors, such as acidity and dissolved organic carbon have been shown to affect the mobilization of mercury and methylation of mercury. Methyl mercury is the most toxic form of this metal and the form most readily accumulated by biota. Thirty-four headwater lakes, selected for a range in pH, were sampled for sediment mercury levels as part of an investigation of the impacts of acid rain on insular Newfoundland lakes. Selected physical and chemical data were also collected on all of the study sites. Acidity was not found to be significantly related to sediment mercury concentrations despite the wide range in pH. Pearson correlation analysis indicated that sediment mercury level was positively correlated with WA:LA (watershed to lake area ratio). WA:LA was also correlated with Secchi depth and colour. Linear regression was used to estimate the parameters of a model relating sediment mercury to WA:LA. Watershed area to lake area ratio was more important than site specific factors in governing the concentration of sediment mercury in lakes without industrial input.     

Influence of Sediment Preservation on Total Mercury and Methylmercury Analyses

Estuarine and riverine sediments from fourlocations showing different sediment structures wereanalysed as fresh, thawed and lyophilised samples fortotal mercury (TotHg) and methylmercury (MeHg)concentrations, and results were compared to addresseffects of sample preservation on Hg speciation. TotHg was measured by cold vapour atomic absorptionspectrometry (CVAAS). MeHg was isolated bydistillation and ion-exchange and analysed by coldvapour atomic fluorescence spectrometry (CVAFS) afterpreconcentration on a gold trap. No loss of TotHg norMeHg due to lyophilisation was found. Concentrationsof TotHg and MeHg respectively ranged from 92 to 267ng g^-1 dw and 1.1 to 2.9 ng g^-1 dw in freshsamples, from 94 to 215 ng g^-1 dw and 1.1 to 2.8ng g^-1 dw in thawed samples, and from 100 to 256ng g^-1 dw and 1.2 to 3.1 ng g^-1 dw inlyophilised samples. Lyophilised samples showedbetter homogeneity and better MeHg analysisreproducibility compared with wet samples.     

Stores from old reservoirs: Sediment Hg and Hg methylation in Ontario hydroelectric developments

We sampled several Ontario Hydro reservoirs to deteimine the changes in mercury (Hg) and organic profiles of sediment cores with reservoir development We also examined Hg methylation among reservoirs of different age and water chemistry. In sediment cores from four Ontario reservoirs, reservoir (watershed) specific differences appeared to supersede general trends, with the differences between headpond and run-of-river reservoirs particularly important In general, the rate of Hg and organic accumulation appeared to increase with reservoir impoundment, but we were unable to discern consistent changes in concentrations of Hg or loss on ignition (LOI) with reservoir impoundment We also observed significant positive correlations of sediment Hg with concentrations of chlorophyll derivatives and bacterial photopigments. Our results are in agreement with earlier studies which indicated that an increase in Hg supply caused by erosion and release from flooded soils is central to the changes in Hg dynamics within reservoirs following impoundment Although Hg methylation activity of sediments, from a series of reservoirs on the Mississagi River was positively correlated with organic content of the sediment, the observed rates were sufficiently variable that the potential effects of reservoir age or preparation methods could not be resolved. Similarly, in our measurements of net methylmercury (MeHg) flux in two older reservoirs, the large range of variation in net MeHg flux observed among replicate samples obscured the potential effects of differences in geology and water chemistry. Future studies should focus on resolving the underlying causes of this variability and in consolidating the ‘microscale’ measurements obtained using sediment core incubation techniques and the ‘macroscale’ values obtained by whole lake mass balance techniques.     

Simple combustion-vapor trapping technique for determination of mercury in fish

A simple combustion train was constructed for analyzing mercury in fish samples. A nitric acid trap was used to capture the mercury vapors which were released later by adding a tin salt. The method is rapid, accurate, and reproducible and permits one person to analyze 40 samples daily. Sample matrix had no apparent effect on the recovery of mercury. Mean recoveries from fish samples spiked with 0.3 and 1.0 microgram mercuric chloride/g ranged from 97 to 105% with an average recovery of 101.5% and a standard deviation of 2.74%.     

Nutrient Removal from Simulated Wastewater Using Canna indica and Schoenoplectus validus in Mono- and Mixed-Culture in Wetland Microcosms

In order to understand the bioaccumulation of mercury in fish in the Iranian coastal waters of the Caspian Sea and the Persian Gulf, different fish species were sampled from both regions in January 2002. Mullet fishes were sampled from the Caspian Sea and six other species from the Persian Gulf: Largetooth flounder, Spotfin flathead, Japanese threadfin bream, Greater lizardfish, Elongate sole and Giant seacatfish. In the Persian Gulf, total Hg concentrations in fish ranged from 0.0123 to 0.0867 mg kg^?1 w.w. (0.0614 to 0.433 mg kg^?1 d.w.). Methylmercury accounts for 64–100% of the total mercury. Highest mercury concentrations were observed in the predatory fish: Giant seacatfish, Threadfin bream and the larger Greater lizardfish caught near Mogham Port. In these species the methylmercury fraction is always higher than 90%. A low methylmercury fraction was only observed in the smallest specimen of flounder and Elongate sole. In the Caspian Sea Hg concentrations in Mullet ranged from 0.0102 to 0.108 mg kg^?1 w.w. The observed concentrations are comparable to those found in other areas of the Persian Gulf as well as in other marine environments and are much lower then the WHO guideline of 0.5 mg kg^?1 w.w.     

MODELLING LEACHING OF INORGANIC Hg(II) IN A SCANDINAVIAN IRON-HUMUS PODZOL - VALIDATION AND LONG-TERM LEACHING UNDER VARIOUS DEPOSITION RATES

Increasing mercury contents are reported from freshwater systems and fish in northern Europe and North America. Mercury input from soils is a major source with the leaching being affected by increased atmospheric mercury deposition compared to pre-industrial times and by other environmental conditions such as acid rain. The results of a mathematical model-calculation of vertical inorganic Hg(II) leaching in a Scandinavian iron-humus podzol under different atmospheric input rates of mercury are presented. Leaching under background rain conditions was calculated to be considerably stronger than under acid rain conditions. Increasing fractions of deposited soluble or solute atmospheric mercury were leached from the O _f(h)-horizon with decreasing soil content of soluble mercury under acid rain conditions; this effect was less pronounced under background rain conditions. The steady state concentrations of soluble mercury of the upper soil horizons were calculated and compared with the actual concentrations of total (= soluble + insoluble mercury) and extractable (= estimate of soluble) mercury measured in these horizons. The results indicate that even if the deposition of airborne mercury to soil is strongly reduced, the total mercury content of the soil decreases only slowly. It may take decades or even centuries before a new steady state concentration of total mercury is established in the soil. The decrease of the mercury concentration in the O _f(h)-horizon is probably largely dependent on the turnover of organic matter, binding most of the deposited airborne mercury in an insoluble form. Hence, present day mercury leaching is likely to be dominated by mercury deposited during former times and temporarily retained in an insoluble form in the organic matter.     

Ultra trace level mercury in the Everglades ecosystem,a multi-media canal pilot study

The Florida Everglades ecosystem is composed of the largest deposit (9600 km²) of near neutral peat in the world extending south of Lake Okeechobee to Florida Bay. The federal Central and South Florida Flood Control Project (C&SF) has sectioned the historic Everglades with a system of canals and levees to control water for urban and agricultural development, resulting in pronounced hydrologic modifications to the natural system. As a part of a comprehensive ecological risk assessment of mercury (Hg) contamination in the Everglades ecosystem, a pilot study of canals was initiated in September 1993 to determine the extent and magnitude of total (HgT) and methylmercury (MeHg) in water, sediment and fish. A probability-based random sampling grid was used to obtain consistent estimates of Hg contamination over this large geographic area. Two hundred canal sampling locations were selected as probability samples by associating grid points on the sampling frame with specific canal sections for independent sampling cycles. Of this number 50 locations were randomly selected for sampling in this pilot study. The selected canal points were sampled from north to south during a six day period. Cumulative distributions with 95% confidence intervals were calculated and used to determine a canal system median concentration for selected water, sediment and fish constituents. The percent exceedance of each median, by hydrologic subarea, was determined to demonstrate the existence and direction of spatial gradients in the system. North to south (high to low) gradients were apparent for total phosphorus (TP), sulfate (SO₄), dissolved organic carbon (DOC), conductance, HgT and MeHg in water. However, the gradients were reversed from south to north for HgT in sediments and fish (Gambusia sp). The greatest Hg concentrations inGambusia sp. occurred in the same canals where largemouth bass had previously been found to be most contaminated.     

Relationships Between Suspended and Sediment Organic Matter in a Semi-Enclosed Marine System: The Stagnone Di Marsala Sound (Western Sicily)

To gather information on the interactions between the sediment and suspended organic matter pools in the Stagnone di Marsala, water and sediment samples were collected, on a monthly basis, at I I stations, Water temperature and salinity showed a clear seasonality whilst particulate and sediment organic matter (lid not show any clear seasonal pattern, Relative abundances of suspended and sediment organic matter, on the other hand. appeared to be site-dependent and controlled mainly by the dynamic balance between resuspension and sedimentation, High quantities of both suspended and sediment total organic matter were present. while very low algal biomasses (in terms of chlorophyll-a concentrations) were observed both in the suspended and sediment pools thus showing the oligotrophy of the site, The contribution of phytoplankton and microphytobenthos to the total organic content of suspended and sediment matter was negligible, The low food availability of organic matter in the Stagnone di Marsala Sound may explain the low abundance of Suspension-feeding molluscs. which are substituted by limnovore and dctritivore species.     

Distribution of Mercury and Other Heavy Metals in Core Sediments of the Northern Adriatic Sea

Seven sediment cores were collected along a transect about20 km off from the mouth of the Po River, in the northernAdriatic Sea (Italy). Cores were characterised by differentdepositional sequences associated with late Pleistocene-Holocene lowstand (LST), transgressive (TST) and highstand (HST) system tracts. Sediment samples were analysed for mercury, copper, nickel, chromium, manganese and iron, aswell as for total organic matter. Metal distributiongenerally showed vertical and spatial variability ascribed tograin size effects with no significant anthropogenicperturbation. Conversely, mercury showed vertical profilescharacterised by surface enrichment, with concentrations inthe upper layer (50–230 ng g^-1) exceeding 3–11 times the background value of 20 ng g^-1 determined in bottomcores. Surface maxima were attributed to anthropogenic mercurydelivered mainly by the Po River.     

Chemical environment of coastal marshes and swamps, Louisiana

Water, sediment and interstitial water in nearshore marshes and swamps along a proposed oil pipeline route in the Louisiana coastal zone were analyzed. The primary objectives were to understand the chemical mechanisms involved and to depict the levels of chemical components in natural environments and in environments altered by man's activities. The brackish and fresh marshes showed the highest organic deposition due to low tidal flushing and runoff rate. High nutrient levels were found in waters of these environments due in part to release from the nutrientladen interstitial water which maintained a dynamic equilibrium with biological activities and organic matter in sediments. Sulfides, expressed as ratio of FeS to organic content was much higher in the saline environment than in the low saline system. Low activities of sulfate reducing microorganisms, limited sulfate and organic-S concentrations in the freshwater environment accounted for the low sulfide level. Impairment of water circulation in the salt marsh resulted in drastic fluctuation in dissolved oxygen and concurrent but inverse changes in sulfide level in sediments and in interstitial NH⁺₄ and PO⁻³₄ in spite of relatively low sediment organic matter. Drainage of fertilizer from agricultural fields and to stagnation in freshwater swamps resulted in persistently lowest dissolved oxygen in swamp water without raising the sulfide level to a great extent in sediment. Detailed discussion on the interrelationships among various factors is presented.     

Development of oxidized odor and volatile aldehydes in fermented cucumber tissue exposed to oxygen

Changes in volatile compounds in fermented cucumber tissue during exposure to oxygen were investigated by purge and trap sampling, followed by GC-MS. Hexanal and a series of trans unsaturated aldehydes, (E)-2-pentenal, (E)-2-hexenal, (E)-2-heptenal, and (E)-2-octenal, increased in fermented cucumber slurries exposed to oxygen. Sensory evaluation of oxidized odor was correlated with the increase in aldehyde concentrations. Other identified volatile components present after fermentation did not show major changes during exposure to oxygen. There was no decrease in the formation of aldehydes in fermented cucumber samples that were heated to inactivate enzymes before exposure to oxygen. These results indicated that the formation of aldehydes in oxygen was due to nonenzymatic reactions.     

Mercury Cycling in Lake Gordon and Lake Pedder,Tasmania (Australia). II: Catchment Processes

The sources and concentrations of total mercury (total Hg) and methylmercury (MeHg) in the upper catchment of the Lake Gordon/Lake Pedder system in Tasmania, Australia were investigated. The catchment area, which contains over 50% wetlands, is located in a temperate region with no obvious point sources of mercury. Surface waters in the region had concentrations of total Hg ranging from 1.2 to 14.4 ng L^-1 and MeHg from < 0.04 to 1.4 ng L^-1. MeHg concentrations were seasonally dependent, with the highest concentrations occurring in summer. Sediments/soils in the catchment had concentrations of total Hg ranging from 4.0 to 194 ng g^-1 and MeHg from <0.02 to 20.1 ng g^-1. The low concentrations of total Hg confirmed that this region is pristine as regards mercury and has no geological enrichment of total Hg. The highest total Hg and MeHg concentrations in both sediment/soils and waters were found in bogs whereas the lowest concentrations typically occurred on the wetlandplains. MeHg concentrations, in bog and swamp sediments were correlatedwith the organic matter content (r = 0.942, P < 0.001). Acid volatile sulfide (AVS) measurements indicate that in most sediments AVS was greater than total Hg. Given the high reactivity of inorganic mercury and sulfide, this suggests that most of the particulate mercury in sediments is present as mercuric sulfide. The yield of MeHg from the catchment was estimated to be 3.2 mg ha^-1 yr^-1 and is higher than published rates measured in non-contaminated temperate catchments in the northern hemisphere. The higher yield was attributed to the generally warmer climatic conditions that favour net methylation and the relatively high rainfall (2–3 m yr^-1) of the region, which supplies reactive inorganic mercury to the active zones ofmercury methylation and also flushes MeHg from the catchment.     

Methylmercury accumulation in rice (Oryza sativa L.) grown at abandoned mercury mines in Guizhou, China

Mercury is a global pollutant that can transform into methylmercury, a highly toxic and bioaccumulative organic form. Previous surveys have shown that fish is the main source of human methylmercury exposure, whereas most other food products have an average value below 20 microg/kg and primarily in the inorganic form. This paper reports that methylmercury in rice (Oryza sativa L.) grown at abandoned mercury mining areas contained levels >100 microg/kg in its edible portion and proved to be 10-100 times higher than other crop plants. The daily adult intake of methylmercury through rice consumption causes abnormally high methylmercury exposure to humans. The results demonstrate that rice is a methylmercury bioaccumulative plant and the main methylmercury source for human exposure in the areas studied.     

Mercury and Organic Carbon Dynamics During Runoff Episodes from a Northeastern USA Watershed

Mercury and organic carbon concentrations vary dynamically in streamwater at the Sleepers River Research Watershed in Vermont, USA. Total mercury (THg) concentrations ranged from 0.53 to 93.8 ng/L during a 3-year period of study. The highest mercury (Hg) concentrations occurred slightly before peak flows and were associated with the highest organic carbon (OC) concentrations. Dissolved Hg (DHg) was the dominant form in the upland catchments; particulate Hg (PHg) dominated in the lowland catchments. The concentration of hydrophobic acid (HPOA), the major component of dissolved organic carbon (DOC), explained 41–98% of the variability of DHg concentration while DOC flux explained 68–85% of the variability in DHg flux, indicating both quality and quantity of the DOC substantially influenced the transport and fate of DHg. Particulate organic carbon (POC) concentrations explained 50% of the PHg variability, indicating that POC is an important transport mechanism for PHg. Despite available sources of DHg and wetlands in the upland catchments, dissolved methylmercury (DmeHg) concentrations in streamwaters were below detection limit (0.04 ng/L). PHg and particulate methylmercury (PmeHg) had a strong positive correlation (r ²?=?0.84, p?<?0.0001), suggesting a common source; likely in-stream or near-stream POC eroded or re-suspended during spring snowmelt and summer storms. Ratios of PmeHg to THg were low and fairly constant despite an apparent higher methylmercury (meHg) production potential in the summer. Methylmercury production in soils and stream sediments was below detection during snowmelt in April and highest in stream sediments (compared to forest and wetland soils) sampled in July. Using the watershed approach, the correlation of the percent of wetland cover to TmeHg concentrations in streamwater indicates that poorly drained wetland soils are a source of meHg and the relatively high concentrations found in stream surface sediments in July indicate these zones are a meHg sink.