Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Total mercury levels in nine species of freshwater fish from two hydroelectric reservoirs and a crater lake in Ghana

Total mercury (Hg) concentrations were determined in the muscle tissue of fish from three reservoirs in Ghana, namely, Lake Bosomtwi, Kpong and Akosombo Hydroelectric Reservoirs. A total of 165 fish samples covering nine species were collected and analysed for total mercury. A mixture of HNO3, H2SO4 and HClO4 were used for complete oxidation of organic tissues. Hg was detected by the Cold Vapour Atomic Absorption Spectrometry technique using an automatic mercury analyzer. Total mercury concentrations in microg g(-1) (wet weight) ranged from below 0.001 to 0.070 for fish from Lake Bosomtwi, 0.010 to 0.275 for fish from Kpong Reservoir and from below 0.001 to 0.042 for fish from Akosombo Reservoir. All the results obtained are below the World Health Organization limit of 0.5 microg g(-1). The low levels of total mercury obtained in this study suggest that the three aquatic environments have not been significantly impacted by mercury contamination.     

Potential risks of natural mercury levels to wild predator fish in an Amazon reservoir

Mercury (Hg) is a toxic metal that bioaccumulates in aquatic organisms and along food chain. Many studies have reported the problem of mercury exposure in aquatic systems from Amazon basin, but very few have focused on the potential risks to wild fish. The present study reports the bioaccumulation of mercury and alterations in target organs of the predator fish Hoplias malabaricus (traíra) from Samuel reservoir, Amazon basin, Northern Brazil. About 18% of fish had mercury levels in muscle exceeding the safe limit for ingestion through food, established by WHO (0.5 μg Hg g(-1)). Fish were separated in two groups according to mercury bioaccumulation in liver (<0.2 μg Hg g(-1)-group I and >0.2 μg Hg g(-1)-group II) for biomarker comparisons. Catalase activity and number of macrophage centers were statistically higher in group II, confirming the potential of Hg to interfere with redox balance and to recruit defense cells to the liver. Conversely, erythrocyte nuclear alterations were less frequent in group II, indicating a more rigorous selection of erythrocytes or hormesis pattern of response. Glutathione S-transferase activity, lipid peroxidation, and histopathological analyses were not statistically different in the liver and gills of both groups. Comparison of lipid peroxidation levels of these fish with others captured in Southern Brazil during another study and the high incidence of morphological alterations in the liver and gills suggest that the bioaccumulation of mercury during continuous exposure is posing potential risks to the species.     

Monitoring cyclical air/water elemental mercury exchange

Previous experimental work has demonstrated that elemental mercury evasion from natural water displays a diel cycle; evasion rates during the day can be two to three times evasion rates observed at night. A study with polychlorinated biphenyls (PCBs) found that diurnal PCB air/water exchange rates exceeded nocturnal exchange rates by 32%. Given that the exchange rates of both PCBs and elemental mercury are dominated by the resistance in the aqueous thin film at the air/water interface and that water column elemental mercury concentrations in natural water bodies also display a diel cycle (and water column PCB concentrations do not) the findings here suggest that PCBs can serve as a tracer to assess the relative contribution of diel atmospheric temperature variations on elemental mercury air/water exchange rates. Using previously published data describing water column elemental mercury concentrations and the previously published diel mercury evasion model, four evasion scenarios are examined within the context of monitoring air/water toxicant exchange: constant atmospheric temperatures and constant water column elemental mercury concentrations; variable atmospheric temperatures and constant water column elemental mercury concentrations; constant atmospheric temperatures and variable water column elemental mercury concentrations; and variable atmospheric temperatures and variable water column elemental mercury concentrations. A scenario of monthly elemental mercury air/water exchange also is examined (at constant atmospheric and water column elemental mercury concentrations). Some of the findings include: (1) atmospheric temperature variations do have a significant effect on air/water toxicant exchange; (2) diel atmospheric temperature variations become more significant to overall diel toxicant exchange rates the closer the air/water system is to equilibrium conditions; (3) for refractory toxicants, average diel exchange rates are best estimated by averaging datasets obtained over a 24 h period or, at minimum, by measuring exchange rates at average atmospheric temperature values; (4) for elemental mercury, variable diel water column concentrations are likely to be the dominant contributor to variations in diel evasion rates; (5) diel atmospheric temperature variations amplify the magnitudes of both diel mercury evasion and absorption events and can shift maximum evasion rates to later in the day; (6) variations in monthly elemental mercury air/water exchange rates may exceed diel variations: and (7) 24 h and monthly monitoring efforts will likely be required to accurately describe diel and annual elemental mercury air/water exchange in a given system.     

Application of neural-based modeling in an assessment of pollution with mercury in the middle part of the Warta River

The level of pollution with various mercury species (organomercury, water- and acid-soluble mercury, mercury bound to humic matter and to sulphides) of the floodplain soils and sediments from middle part of the Warta River has been assessed using self-organizing maps (SOM). Chemometric evaluation allowed identification of moderately (median 173-187 ng g(-1), range 54-375 ng g(-1) in soil and 130 ng g(-1), range 47-310 ng g(-1) in sediment) and heavily polluted samples (662 ng g(-1), range 426-884 ng g(-1)). Heavily polluted were located mainly below and in the area of the Poznań city. Statistical comparison of mercury species distribution in floodplain soils of the Warta River shows different patterns for moderately and heavily polluted samples. In heavily polluted soils the contribution of mobile mercury (sum of organomercury species, water- and acid soluble species) is lower (4.2%) than in moderately polluted soils (6.1%). Higher contribution of mobile mercury was observed in sediments of the Warta River (12%). In case of moderately polluted samples, statistical differences in the contribution of mercury species are relatively low and thus the environmental risk from mercury deposited in aquatic system of the Warta River is relatively low. However, higher water levels and heavy floods may incite remobilisation of some organomercuries (2.2-2.9 ng g(-1) in soil and 10 ng g(-1) in sediment) and acid-soluble species of mercury (2.6-2.9 ng g(-1) in soil and 0.5 ng g(-1) in sediment).     

Estuarine mixing behavior of colloidal organic carbon and colloidal mercury in Galveston Bay, Texas

Mercury (Hg) in estuarine water is distributed among different physical phases (i.e. particulate, colloidal, and truly dissolved). This phase speciation influences the fate and cycling of Hg in estuarine systems. However, limited information exists on the estuarine distribution of colloidal phase Hg, mainly due to the technical difficulties involved in measuring it. In the present study, we determined Hg and organic carbon levels from unfiltered, filtered (<0.45 μm), colloidal (10 kDa-0.45 μm), and truly dissolved (<10 kDa) fractions of Galveston Bay surface water in order to understand the estuarine mixing behavior of Hg species as well as interactions of Hg with colloidal organic matter. For the riverine end-member, the colloidal fraction comprised 43 ± 11% of the total dissolved Hg pool and decreased to 17 ± 8% in brackish water. In the estuarine mixing zone, dissolved Hg and colloidal organic carbon showed non-conservative removal behavior, particularly in the low salinity (<15 ppt) region. This removal may be caused by salt-induced coagulation of colloidal matter and consequent removal of dissolved Hg. The particle-water interaction, K(d) ([particulate Hg (mol kg(-1))]/[dissolved Hg (mol L(-1))]) of Hg decreased as particle concentration increased, while the particle-water partition coefficient based on colloidal Hg and the truly dissolved Hg fraction, K(c) ([colloidal Hg (mol kg(-1))]/[truly dissolved Hg (mol L(-1))]) of Hg remained constant as particle concentration increased. This suggests that the particle concentration effect is associated with the amount of colloidal Hg, increasing in proportion to the amount of suspended particulate matter. This work demonstrates that, colloidal organic matter plays an important role in the transport, particle-water partitioning, and removal of dissolved Hg in estuarine waters.     

Development of a novel passive sampling system for the time-averaged measurement of a range of organic pollutants in aquatic environments

A new sampling system has been developed for the measurement of time-averaged concentrations of organic micropollutants in aquatic environments. The system is based on the diffusion of targeted organic compounds through a rate-limiting membrane and the subsequent accumulation of these species in a bound, hydrophobic, solid-phase material. It provides a novel and robust solution to the problem of monitoring in situations where large temporal fluctuations in pollutant levels may occur. Accumulation rates are regulated by choice of diffusion-limiting membrane and bound solid-phase material and have been found to be dependent on the physico-chemical properties of individual target analytes. Two separate prototype systems are described: one suitable for the sampling of non-polar organic species with log octanol/water partition coefficient (log P) values greater than 4, the other for more polar species with log P values between 2 and 4. Both systems use the same solid-phase material (47 mm C18 Empore disk) as a receiving phase but are fitted with different rate-limiting membrane materials (polysulfone for the polar and polyethylene for the non-polar analytes). The two systems complement each other and together can be used for sampling a wider range of organic analytes than generally possible using current passive sampling techniques. Calibration data are presented for both devices. In each case, linear uptake kinetics were sustained, under constant conditions, for deployment periods of between 1 and 9 days. The effects of water temperature and turbulence on sampling rates have been quantitatively assessed. The performance of the system was further investigated by means of field exposures for one and two weeks in marine environments where calibrated samplers were used to determine the time-averaged concentrations of the polar biocides diuron and irgarol 1051. The quantitative results obtained using the passive sampler were compared with those obtained using spot sampling.     

Investigations of mercury concentrations in walleye and other fish in the Athabasca River ecosystem with increasing oil sands developments

Recent studies have reported an increasing trend of mercury concentrations in walleye (Sander vitreus) from the Athabasca River, north eastern Alberta (Canada); these studies were based on three years of comparison and attributed the mercury increase to expanding oil sands developments in the region. In order to conduct a more comprehensive analysis of mercury trends in fish, we compiled an extensive database for walleye, lake whitefish (Coregonus clupeaformis), northern pike (Esox lucius) and lake trout (Salvelinus namaycush) using all available data obtained from provincial, federal, and industry-funded monitoring and other programs. Evidence for increasing trends in mercury concentrations were examined for each species by location and year also considering fish weight and length. In the immediate oil sands area of the Athabasca River, mercury concentrations decreased (p < 0.001) in walleye and lake whitefish over 1984-2011. In western Lake Athabasca and its delta, mercury concentrations decreased (p < 0.0001) in northern pike (1981-2009) although no trend was evident for walleye (1981-2005) and lake trout (1978-2009). Mercury concentrations in lake trout from Namur Lake, a small lake west of the oil sands area, were higher in 2007 than 2000 (p < 0.0001); it is difficult to ascribe this increase to an oil sands impact because similar increases in mercury concentrations have been observed in lake trout from similar sized lakes in the Northwest Territories. While mercury emissions rates have increased with oil sands development and the landscape become more disturbed, mercury concentrations remained low in water and sediments in the Athabasca River and its tributaries and similar to concentrations observed outside the development areas and in earlier decades. Our fish database was assembled from a series of studies that differed in study purpose, design, and analytical methods. Future monitoring programs investigating mercury trends in fish should be more rigorous in their design.     

A comparison of data quality control protocols for atmospheric mercury speciation measurements

Significant advances in the measurement of atmospheric mercury species have been made in the past 10 years yet limited protocols on quality control (QC) and assurance on this data have been published in the literature. Recently, considerable work has been done to develop quality control and assurance programs within North America. Environment Canada and the National Atmospheric Deposition Network (NADP) independently developed programs, RDMQ? and AMQC, respectively, to QC atmospheric mercury speciation data (including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated to particles (PHg)). These 2 programs were assessed by the criteria on which the data is QCed and comparability of the final data products. Results show that the criteria used to flag data compare well within the 4 tested sites and that the number of flags for each criterion is generally comparable. The QC programs were applied to 2 distinct data sets and the final QCed data was compared. From a mid-latitude site, the final data sets compare very well and showed there to be a 0.3, 8.6 and 15% difference in the mean GEM, RGM and PHg concentrations post QC of each program. It is recommended that either the RDMQ or the AMQC programs be employed for a typical mid-latitude site. When the QC programs were applied to highly variable data, the data do not compare as well for RGM and PHg. Results showed a 2.7, 27 and 33% difference in the mean GEM, RGM and PHg concentrations, respectively, post QC of each program. It is recommended that RDMQ be used for data that is highly variable with high RGM/PHg concentrations as it allows for more manual correction over the QCed data. This investigation of 2 QC programs produced comparable data and that either of these programs can be used as standard methods for the quality control of atmospheric mercury speciation data.     

Fractions and leaching characteristics of mercury in coal

A huge amount of coal is always stored in open spaces in coal-fired power plants before combustion. Mercury released from coal by rain or flowing water is an environmental risk and can cause contamination of the soil around the storage area. To better understand mercury pollution and to control mercury emission before combustion, it is necessary to determine the mobility and leaching characteristics of mercury from coal. In this study, we collected ten coal samples from one coal-fired power plant and proposed a sequential extraction procedure to get five fractions of mercury for evaluation. Elemental Hg was found as the most dominant fraction, and sulfate Hg was shown to be the second largest fraction. The mercury in the organic and the soluble fractions were not the major fractions, but they should still be considered because of their high mobility.     

Remediation aspect of microbial changes of plant rhizosphere in mercury contaminated soil

Phytoremediation, an approach that uses plants to remediate contaminated soil through degradation, stabilization or accumulation, may provide an efficient solution to some mercury contamination problems. This paper presents growth chamber experiments that tested the ability of plant species to stabilize mercury in soil. Several indigenous herbaceous species and Salix viminalis were grown in soil collected from a mercury-contaminated site in southern Poland. The uptake and distribution of mercury by these plants were investigated, and the growth and vitality of the plants through a part of one vegetative cycle were assessed. The highest concentrations of mercury were found at the roots, but translocation to the aerial part also occurred. Most of the plant species tested displayed good growth on mercury contaminated soil and sustained a rich microbial population in the rhizosphere. The microbial populations of root-free soil and rhizosphere soil from all species were also examined. An inverse correlation between the number of sulfur amino acid decomposing bacteria and root mercury content was observed. These results indicate the potential for using some species of plants to treat mercury contaminated soil through stabilization rather than extraction. The present investigation proposes a practical cost-effective temporary solution for phytostabilization of soil with moderate mercury contamination as well as the basis for plant selection.     

Total mercury status in an urban water body,Mithi River,Mumbai and analysis of the relation between total mercury and other pollution parameters

Mercury is a heavy metal which has garnered attention recently in India. Minamata Convention on mercury was established on October 2013 and was joined by India on September 30, 2014. India is seen as a major mercury pollution source after China according to many studies in the past. Various mercury pollution sites that are currently recognized in India are Kodai Lake, Kodaikanal, Tamil Nadu, and Thane Creek, Mumbai. Since 1992, chlor-alkali plants have been regulated to eliminate mercury cell process of manufacturing. Also, medical and health care facilities are discarding mercury-containing equipment and processes. Various anthropogenic sources of mercury to the atmosphere include combustion of fossil fuels, processing and mining of primary metal ores, cement manufacturing units, chlor-alkali plants, and use of mercury in various products like paints, electric switches, and relays. The hazard associated with mercury pollution becomes extremely serious when we consider its ability to be transported over long-range distances. Various atmospheric transport models suggest India and other Asian countries to be a major source of long-range transport of mercury to North America. Considering the hazards of mercury and its widespread presence in our life, a study on mercury pollution in an urban water body is conducted. This study deals with Mithi River located in Mumbai Metropolitan Region (19.0760° N, 72.8777° E) to study the total mercury in water and derive its relationship with other pollution parameters.     

Importance of eating habits and sample size in the estimation of environmental mercury contamination using biological indicators

The importance of eating habits and the number of fish sampled in the estimation of mercury environmental contamination through biological indicators was studied. The species used were one with piscivorous habits (Anguilla anguilla) and another with omnivorous habits (Ciprinus carpio). From one original sample for each species, randomized samples were generated using the subroutine GGSRS from the mathematics library IMSL, and later the statistical significance of Pearson's correlation coefficient for the relationship between fish weight and mercury concentrations in muscle was obtained for each random sample. The results show that the use of omnivorous species such as Ciprinus carpio as a biological indicator of contamination enables us to carry out estimations with a greater degree of confidence than when piscivorous species such as Anguilla anguilla are used.     

Methyl mercury in fish—a case study on various samples collected from Ganges river at West Bengal

This study investigated the presence of total mercury (Hg) and organic mercury levels in the muscle of 19 common fresh water fish species captured from river Ganges, West Bengal, India. The total mercury level found in our study may not cause any toxic effect, but the methyl mercury (MeHg) level in some freshwater fish species was surprisingly very high and toxically unacceptable. The results of mercury analysis in various specimens indicated that some fish muscles tended to accumulate high levels of Hg, and approximately 50–84% of Hg was organic mercury. A strong positive correlation between mercury levels in muscle with food habit and fish length (age) was found. Wallago attu possessed the highest amount of organic mercury in their muscle tissues, and it was 0.93 ± 0.61 μg Hg/g of wet weight. Whereas in small-sized fishes Eutropiichthys murius, Puntius sarana, Cirrhinus mrigala, Mystus vittatus or Mystus gulio, and Tilapia mossambicus, it was below the detection limit. Contamination in Catla catla (0.32 ± 0.11), Anguilla bengalensis bengalensis (0.26 ± 0.07 μg Hg/g), Chitala chitala (0.25 ± 0.18), Rita rita (0.34 ± 0.14), and Ompok pabda (0.26 ± 0.04) was also above the 0.25 μg Hg/g of wet weight, the limit set by the PFA for the maximum level for consumption of fish exposed to MeHg. Though in Labeo rohita (0.12 ± 0.03), Mastacembelus armatus (0.17 ± 0.02), Pangasius pangasius (0.12 ± 0.16), Bagarius bagarius (0.12 ± 0.01), and Clupisoma garua (0.1 ± 0.01), concentration was below the recommended level, in Lates calcarifer (0.23 ± 0.0) and Mystus aor (0.23 ± 0.1), it was threatening. Interestingly, a low concentration of Hg was found in post-monsoon samples.     

Speciation of mercury in mine waste: case study of abandoned and active gold mine sites at the Bibiani–Anwiaso–Bekwai area of South Western Ghana

Speciation determines toxicity, transport pathways and residence time of a metal in different compartments of the environment. This study investigated the speciation of mercury in soils, derived from sites known for dumping of mine wastes in the Bibiani–Anwiaso–Bekwai district, a gold mining community of the Western Region of Ghana. Soil samples were taken from the surface; depths of 20, 40 and 60?cm from mine waste at both abandoned and active mine sites. Each sample was analysed for total mercury, organic mercury and elemental mercury. After sample treatment, digestion and reduction with stannous chloride (SnCl₂), total mercury content was determined using the Inductively Coupled Plasma—Optical Emissions Spectrometer (ICP–OES). Organic mercury content was determined employing a differential technique after disposing of elemental mercury by heating. Total mercury content in samples ranged from 0.067 to 0.876?mg/kg for surface soils. The same soil of depths 20, 40 and 60?cm had total mercury from 0.102 to 1.066, 0.037 to 4.037 and 0.191 to 4.998?mg/kg, respectively. For organic mercury, concentrations range from 0.012 to 0.260?mg/kg for surface soil. Soil depths of 20, 40 and 60?cm had organic mercury concentrations from 0.016 to 0.653, 0.041 to 1.093 and 0.101 to 2.546?mg/kg respectively. Elemental mercury concentrations in surface soils, soils at depths of 20, 40 and 60 cm ranged from 0.043 to 0.780; 0.017 to 0.749; 0.014 to 2.944 and 0.009 to 2.452 mg/kg respectively. Among the sites studied, only galamsey tailings (GM) showed a trend of increasing total mercury level with increasing depth. For the other sites, trends were not defined. There has been no defined trend for elemental mercury with depth at any of the sampling sites. Just as with total mercury, it was only GM that showed an increasing trend of organic mercury concentration with depth.     

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.     

Total mercury determination in sand boxes from Montreal

Direct mercury analysis was successfully applied to determine trace levels of total mercury in samples from sand boxes in Montréal (Québec, Canada). Twenty sand boxes were sampled from across the city and divided into two size fractions, a fine fraction (<100 microm) and a whole fraction. The concentrations of mercury ranged from 1.6 to 35 microg Hg kg(-1) dry soil for the fine fraction and from 0.7 to 6 microg Hg kg(-1) dry soil for the whole fraction. The mercury concentrations correlated with the soil organic carbon content (R2= 0.67) in the sand. The ratio of the concentration of mercury in the fine over the whole fraction varied from 2.2 to 18. Using published soil ingestion rates for children, the calculated daily intake values varied from 0 to 0.5 ng Hg kg(-1) bw d(-1) with an estimated oral ingestion of 200 mg of sand and from 0.2 to 4.7 ng Hg kg(-1) bw d(-1) with an ingestion of 1750 mg of sand. None of the sand boxes contain sufficient amounts of mercury so as to exceed the currently accepted daily intake threshold of 0.105 microg Hg kg(-1) bw d(-1) established by Health Canada.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.