Studies on the influence of CN on Hg methylation rates in aquatic systems draining gold mining (artisanal and small-scale) communities in Africa are rare. The study assessed the influence of CN on Hg ...methylation in aquatic sediments of two major river systems draining artisanal and small-scale gold mining (ASGM) communities of the Prestea-Huni Valley district, Southwestern Ghana. The miners extract gold (Au) through exclusive amalgam Hg-Au formation or cyanidation of Au-rich Hg-contaminated tailings, or a combination of both techniques. Hg water solubility and probable mercuric compounds in sediments of Hg-contaminated CN-loaded (River Aprepre) and Hg-contaminated non-CN (River Ankobra) aquatic systems within the district were investigated. THg was determined by CV-AAS after HF/HNO
3
/HCl digestion. MeHg in sediments were extracted with H
2
SO
4
/KBr/CuSO
4
-CH
2
Cl
2
; followed by aqueous-phase propylation, preconcentration-on-Tenax, and GC-CV-AFS. River Aprepre showed 4.58–14.83 ngMeHg/g as Hg (1.4–3.7% THg as MeHg), with 241–415 ngTHg/g, and 0.05–0.21 mgCN/kg. For River Ankobra, MeHg ranged 0.24–1.21 ngMeHg/g (0.08–0.35% THg as MeHg) with 162–490 ngTHg/g dw and CN < 0.001 mg/kg. There was positive correlation (
r
2
= 0.5974;
p
< 0.01) between MeHg and CN in River Aprepre. The water-soluble fraction of Hg in sediment from both rivers was < 1% of THg. Hg in sediments from River Aprepre were generally more soluble than that from River Ankobra, indicating that Hg in sediments from River Aprepre were potentially more bioavailable for methylation. Accordingly, the presence of CN in Hg-dominated river sediments potentially influences and enhances the solubility and mobility of Hg, resulting in increased Hg methylation rates.
The distributions of the total mercury (T-Hg), methylmercury (MeHg), and ethylmercury (EtHg) concentrations in soil and their relationship to chemical composition of the soil and total organic carbon ...content (TOC, %) were investigated. Core samples were collected from hill slope on the right and left riverbanks of the Idrija River. Former smelting plant is located on the right bank. The T-Hg average in each of the core samples ranged from 0.25 to 1650 mg kg−1. The vertical T-Hg variations in the samples from the left bank showed no significant change with depth. Conversely, the T-Hg varied with depth, with the surface, or layers several centimeters from the surface, tending to show the highest values in the samples from the right bank. Since the right and left bank soils have different chemical compositions, different pathways of mercury delivery into soils were suggested. The MeHg and EtHg concentrations ranged from n.d. (not detected) to 444 μg kg−1 and n.d. to 17.4 μg kg−1, respectively. The vertical variations of MeHg and EtHg were similar to those of TOC, except for the near-surface layers containing TOC greater than 20%. These results suggest that the decomposition of organic matter is closely related to organic mercury formation.
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•The distributions of T-Hg, MeHg, and EtHg near the Idrija Hg mine were investigated.•The Hg values were compared to the chemical composition, TOC, and T-N of the soil.•The first data of EtHg in soil around the mine is reported.•The decomposition of organic matter is closely related to organic Hg formation.•Hg circulation among soil, air and plant with change of chemical forms was suggested.
The province of Guizhou in Southwestern China is currently one of the world's most important mercury production areas. Emissions of mercury from the province to the global atmosphere have been ...estimated to be approximately 12% of the world total anthropogenic emissions. The main objective of this study was to assess the level of contamination with Hg in two geographical areas of Guizhou province. Mercury pollution in the areas concerned originates from mercury mining and ore processing in the area of Wanshan, while in the area of Quingzhen mercury pollution originates from the chemical industry discharging Hg through wastewaters and emissions to the atmosphere due to coal burning for electricity production. The results of this study confirmed high contamination with Hg in soil, sediments and rice in the Hg mining area in Wanshan. High levels of Hg in soil and rice were also found in the vicinity of the chemical plant in Quingzhen. The concentrations of Hg decreased with distance from the main sources of pollution considerably. The general conclusion is that Hg contamination in Wanshan is geographically more widespread, due to deposition and scavenging of Hg from contaminated air and deposition on land. In Quingzhen Hg contamination of soil is very high close to the chemical plant but the levels reach background concentrations at a distance of several km. Even though the major source of Hg in both areas is inorganic Hg, it was observed that active transformation of inorganic Hg to organic Hg species (MeHg) takes place in water, sediments and soils. The concentration of Hg in rice grains can reach up to 569 μg/kg of total Hg of which 145 μg/kg was in MeHg form. The percentage of Hg as MeHg varied from 5 to 83%. The concentrations of selenium can reach up to 16 mg/kg in soil and up to 1 mg/g in rice. A correlation exists between the concentration of Se in soil and rice, indicating that a portion of Se is bioavailabile to plants. No correlation between Hg and Se in rice was found. Exposure of the local population to Hg may occur due to inhalation of Hg present in air (in particular in Hg mining area) and consumption of Hg contaminated food (in particular rice and fish) and water. Comparison of intake through these different routes showed that the values of Hg considerably exceed the USA EPA Reference Concentration (RfC) for chronic Hg exposure (RfC is 0.0004 mg/m
3) close to the emission sources. Intake of Hg through food consumption, particularly rice and fish, is also an important route of Hg exposure in study area. In general, it can be concluded that the population mostly at risk is located in the vicinity of smelting facilities, mining activities and close to the waste disposal sites in the wider area of Wanshan. In order to assess the real level of contamination in the local population, it is recommended that biomonitoring should be performed, including Hg and MeHg measurements in hair, blood and urine samples.
This work reports the development of ultralight interwoven ultrathin graphitic carbon nitride (g-CN) nanosheets for use as a potential adsorbent in a passive sampler (PAS) designed to bind Hg2+ ions. ...The g-CN nanosheets were prepared from bulk g-CN synthesised via a modified high-temperature short-time (HTST) polycondensation process. The crystal structure, surface functional groups, and morphology of the g-CN nanosheets were characterised using a battery of instruments. The results confirmed that the as-synthesized product is composed of few-layered nanosheets. The adsorption efficiency of g-CN for binding Hg2+ (100 ng mL−1) in sea, river, rain, and Milli-Q quality water was 89%, 93%, 97%, and 100%, respectively, at natural pH. Interference studies found that the cations tested (Co2+, Ca2+, Zn2+, Fe2+, Mn2+, Ni2+, Bi3+, Na+, and K+) had no significant effect on the adsorption efficiency of Hg2+. Different parameters were optimised to improve the performance of g-CN such as pH, contact time, and amount of adsorbent. Optimum conditions were pH 7, 120 min incubation time and 10 mg of nanosheets. The yield of nanosheets was 72.5%, which is higher compared to other polycondensation processes using different monomers. The g-CN sheets could also be regenerated up to eight times with only a 20% loss in binding efficiency. Overall, nano-knitted g-CN is a promising low-cost green adsorbent for use in passive samplers or as a transducing material in sensor applications.
An inter-laboratory study was conducted to compare results from different analytical methods for monomethylmercury (MeHg) concentrations in 17 soil and sediment samples. The samples were collected ...from mercury-contaminated areas, including Minamata Bay and Kagoshima Bay in Japan, the Idrija mercury mine in Slovenia, and an artisanal small-scale gold mining area in Indonesia. The Hg in these samples comes from several different sources: industrial waste from an acetaldehyde production facility, volcanic activity, Hg mining activity, and artisanal and small-scale gold mining activity (ASGM). MeHg concentrations in all the samples were measured in four separate laboratories, using three different determination methods: Kagoshima University (Japan), using high-performance liquid chromatography–chemiluminescence detection (HPLC-CL); National Institute for Minamata Disease (Japan), using gas chromatography–electron capture detection; and Metropolitan Council Environmental Services (USA) and Jozef Stefan Institute (Slovenia), both using alkylation-gas chromatography–atomic fluorescence spectrometry detection. The methods gave comparable MeHg results for most of the samples tested, but for some samples, the results exhibited significant variability depending on the method used. The HPLC-CL method performed poorly when applied to samples with elevated sulfur concentrations, producing MeHg concentrations that were much lower than those from the other methods. Additional analytical work demonstrated the elimination of this sulfur interference when the method was modified to bind sulfur prior to the analytical step by using Hg2+ as a masking agent. These results demonstrate the value of laboratory intercomparison exercises in contributing to the improvement of analytical methods.
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•Three different methods for the determination of MeHg in soils and sediments were compared in an inter-laboratory study.•The various analytical methods yielded comparable results for most of the soil and sediment samples.•Higher analytical variability was observed for samples containing higher concentrations of S.•The results were used to modify and improve a new liquid chromatography method.
The atmospheric distribution and deposition of Hg in the area of the former Idrija Hg-mine, Slovenia, were investigated. Mapping of air Hg
0 concentrations was performed to assess the spatial ...distribution and major sources of mercury to the atmosphere in the area. In addition, analyses of mercury speciation in the air over Idrija were performed during a 4-day sampling campaign in September 2006 to better understand the fate and transformation of Hg in the atmosphere of this specific mercury polluted site. The speciation results were then compared to the results of mercury speciation in the wet and throughfall deposition sampled on a precipitation event basis from October 2006 to September 2007. The Hg
0 concentration in air was mostly below 10
ng
m
−3, with the highest concentration in the area of the former smelter complex exceeding 5000
ng
m
−3. Mercury-bearing airborne particles (TPM) seem to dominate the atmospheric Hg deposition, which revealed noticeable variations between precipitation events (11–76
ng
m
−2
day
−1), mostly as a function of the amount of precipitation. Hg in precipitation was largely (∼50%) associated with the particulate phase (THg
P). No correlation was found between the THg
P and the dissolved phases (THg
D), suggesting that particulate phase Hg is mostly the result of dry deposition. In the throughfall, significantly higher (2–10 fold) Hg concentrations than in associated event precipitation were observed, mostly due to Hg in the particulate phase (∼70% THg). As shown by SEM/EDXS microscopy, an important amount of mercury in the precipitation and throughfall samples is due to the presence of cinnabar particles as a result of the aeolian erosion of cinnabar-containing surfaces in the area.
► Soils surrounding the smelting plant are the main source of Hg in the Idrija region. ► Atmospheric Hg in the Idrija Hg-mine region is subjected to long range transport. ► Mercury-bearing airborne particles dominate the atmospheric deposition.
Different chemical forms of mercury occur naturally in human milk. The most controversial aspect of early post-natal exposure to organic mercury is ethylmercury (EtHg) in thimerosal-containing ...vaccines (TCV) still being used in many countries. Thus exclusively breastfed infants can be exposed to both, fish derived methylmercury (MeHg) in maternal diets and to EtHg from TCV. The aim of the study is to evaluate a new analytical method for ethyl and methyl mercury in hair samples of breastfed infants who had received the recommended schedule of TCV.
The hair of infants (<12months) that had been exposed to TCV (Hepatitis B and DTaP) was analysed. A method coupling isothermal gas chromatography with cold-vapor atomic fluorescence spectrometry was used for MeHg which can also speciate EtHg in biological matrices.
In 20 samples of infants' hair, all but two samples showed variable amounts of MeHg (10.3 to 668ng/g), while precise and reliable concentrations of EtHg (3.7 to 65.0ng/g) were found in 15 of the 20 samples. A statistically significant inverse association (r=−05572; p=0.0384) was found between hair-EtHg concentrations and the time elapsed after the last TCV shot.
The analytical method proved sensitive enough to quantify EtHg in babies' hair after acute exposure to thimerosal in vaccine shots. Provided that the mass of hair was above 10mg, organic-mercury exposure during early life can be speciated, and quantified in babies' first hair, thus opening opportunities for clinical and forensic studies.
A summary of data recently obtained for mercury analysis and speciation (reactive Hg, total Hg and monomethylmercury (MMHg)) in filtered and non-filtered seawater samples, dissolved gaseous mercury ...(DGM) and dimethylmercury (DMHg) in open and coastal waters of the Mediterranean Sea is presented. The majority of the results were obtained during an oceanographic cruise aboard the research vessel Urania from 14 July to 9 August, 2000, as part of the MED-OCEANOR Project funded by the National Research Council of Italy. The results are compared with those obtained in contaminated coastal environments of the Adriatic (The Gulf of Trieste and Kaštela Bay) and non-contaminated coastal waters of the eastern Adriatic coast obtained in 1998. Total mercury concentrations in surface ocean waters are relatively low with an average of 0.81
pM (0.49–1.91
pM). Reactive Hg represents a substantial part with an average of 57% of total Hg (15–97%). Most mercury in open ocean waters was present in the dissolved form (32–95%, av. 70%), which is mainly due to the low abundance of particulate matter, a phenomenon well known for the Mediterranean open ocean waters. On average the percentage of Hg as MMHg was about 20%, of which about 66% was present in the dissolved form. The percentage of DGM in the surface ocean waters represents about 9% of total Hg (2.5–24.5%) and may originate from photochemical, biologically mediated mechanisms or diffusion from deeper layer either due to biological and/or to tectonic activity which is typical of the Mediterranean region. The presence of DMHg was confirmed only in waters below 20
m (up to 12
fM), while in surface waters DMHg was below the limit of detection (<0.1
fM). Surface concentrations of Hg in the eastern and western parts are comparable, except for DGM which shows significantly higher concentrations in the eastern part (mean value: 0.22
pM) as compared to the western Mediterranean (mean value: 0.09
pM). The distribution of Hg species with depth was only measured at two stations, and indicated variability comparing the eastern and the western leg of the Urania cruise. The depth profile pattern confirms the importance of dynamic processes at the surface layers, while deep water continuously supplies DGM to the surface layer. The importance of analytical quality control is also discussed in this paper.
500 years of mercury (Hg) mining in the town of Idrija has caused severe pollution in Idrija and its surroundings. Following the closure of the mine in 1995, the environment remains contaminated with ...Hg. Sources of elemental-, inorganic- and methyl Hg exposure were identified, potential environmental level of exposure to Hg was evaluated and actual internal exposure to Hg was assessed in selected susceptible population groups comprising school-age children and pregnant women living in Idrija and in control groups from rural and urban environments. The study of pregnant women (n=31) was conducted between 2003 and 2008, and the study of school-age children (n=176) in 2008. Potential interaction of Hg with selenium (Se) in plasma was assessed in both study populations, while in pregnant women antioxidative enzyme activity (glutathione peroxidase, superoxide dismutase and catalase) in erythrocytes of maternal and cord blood was also assessed. Actual exposure to Hg as indicated by levels of Hg in children's blood (geometric mean (GM) 0.92µg/L), mother's blood (GM 1.86µg/L), children's urine (GM 1.08µg/g crea.), mother's urine (GM 2.51µg/L), children's hair (GM 241ng/g) and mother's hair (GM 251ng/g) was higher in the two study groups from Idrija than in the control groups from rural areas, but was still at the level of a “normal” population and reflects mainly exposure to elemental Hg (Hg°) from dental amalgam and, to a certain extent atmospheric Hg°. Furthermore, the internal doses of Hg received during pregnancy did not decrease the bioavailability of Se. Based on observation in children, the increase in Se protein expression is suggested to be a consequence of moderately elevated exposure to Hg°. The observed changes in activity of antioxidative enzymes, as biomarkers of oxidative stress, appear to be mainly associated with pregnancy per se and not with an increased exposure to Hg. In view of the continuing increased potential for Hg exposure and the low number of pregnant women studied, the results warrant a further longitudinal study of a larger group of pregnant women residing in the area of the former mercury mine.
•Estimated environmental Hg exposure in the town of Idrija still poses a potential risk to susceptible groups of inhabitants.•Actual internal exposure reflects mainly exposure to Hg° from dental amalgam and, to a certain extent atmospheric Hg°.•The internal doses of Hg received in the Idrija children and pregnant women did not decrease the bioavailability of Se.•Changes in activity of antioxidative enzymes were not associated with exposure to Hg in the town of Idrija.
Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 ...and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32
±
0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33
±
0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg
0, represents a considerable proportion of THg (average 20%, 0.23
±
0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67
±
2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68
±
0.43 pM and 0.29
±
0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.
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