Enhanced mercury reduction in the South Atlantic Ocean during carbon remineralization.

Mercury (Hg) in seawater is subject to interconversions via (photo)chemical and (micro)biological processes that determine the extent of dissolved gaseous mercury (DGM) (re)emission and the production of monomethylmercury. We investigated Hg speciation in the South Atlantic Ocean on a GEOTRACES cruise along a 40°S section between December 2011 and January 2012 (354 samples collected at 24 stations from surface to 5250 m maximum depth). Using statistical analysis, concentrations of methylated mercury (MeHg, geometric mean 35.4 fmol L-1) were related to seawater temperature, salinity, and fluorescence. DGM concentrations (geometric mean 0.17 pmol L-1) were related to water column depth, concentrations of macronutrients and dissolved inorganic carbon (DIC). The first-ever observed linear correlation between DGM and DIC obtained from high-resolution data indicates possible DGM production by organic matter remineralization via biological or dark abiotic reactions. DGM concentrations projected from literature DIC data using the newly discovered DGM-DIC relationship agreed with published DGM observations.

Mercury methylation in cyanide influenced river sediments: A comparative study in Southwestern Ghana.

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/HNO3/HCl digestion. MeHg in sediments were extracted with H2SO4/KBr/CuSO4-CH2Cl2; 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 (r2 = 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.

Prenatal low-level methyl mercury exposure and child development in an Italian coastal area.

Environmental studies have identified mercury pollution in the Northern Adriatic Sea (Italy). High- level methyl mercury exposure is a known cause of neurodevelopmental disorders. However, the exposure-effect relation at levels <10ppm is controversial. To assess the possible health effects of prenatal methyl mercury exposure through maternal fish consumption, we conducted an epidemiologic cohort study in a mercury polluted area of the Adriatic Sea. We identified all the children born between 1999 and 2001 to women who were resident in two coastal fishing towns. A comparison group was identified inland. A total of 243 children were enrolled. Their mothers were interviewed approximately two months after delivery to determine a variety of covariates and the type, quantity and origin of fish consumed during pregnancy. Total mercury (THg) and methyl mercury (MeHg) were assessed in maternal hair and breast milk and in the child's hair. The children were evaluated after age 18 months with a physical examination and the Denver Developmental Screening Test II (DDST II). Statistical analyses matched by residential area are not presented since they were not associated with fresh fish consumption, THg or MeHg exposure level or neurodevelopmental outcomes. To date 52 children have been evaluated. After adjustment for a number of potential confounders, preliminary results indicate that the fine motor adaptive score on the Denver Developmental test is inversely related to maternal hair THg. These pilot findings are suggestive of an association between children's fine motor skills and their prenatal methyl mercury exposure from maternal fish consumption. However, only a small number of the cohort have been tested and more extensive testing with more sensitive and specific tests is needed to determine if these findings persist.

Mercury speciation in meconium and associated factors.

Meconium is formed early in gestation and it is normally not excreted until after birth. Thus it may provide a longer and cumulative record of exposure to mercury (Hg). The present study aims to speciate Hg in meconium samples (N = 488) from Slovenian and Croatian new-borns prenatally exposed to low levels of methyl-Hg (MeHg) from maternal seafood intake and to Hg0 from maternal dental amalgam fillings. We had complete data of total Hg (THg) and MeHg in meconium and THg in maternal hair (MH), while THg and MeHg in maternal blood (MB) were available only for Croatian mothers. Personal data namely maternal seafood intake, age, pre-pregnancy BMI, parity, smoking, estimated gestational age at birth, sex, and birth weight were available for the majority of participants, except the number of dental amalgams which was in most cases missing for Croatian mothers. The median THg concentration in meconium was 11.1 (range: 0.41-375.2) ng/g and inorganic Hg (Hg(II)) presented 98.8% (range: 82%-100%, CV: 2%) of THg. We observed significant correlation between meconium and MH Hg levels, with the highest correlation between hair THg and meconium MeHg. Correlation analysis including MB (available only for Croatian population) showed a significant positive correlation between THg in meconium and THg in MB (Rs = 0.642). Additionally, MeHg from MB was correlated with MeHg in meconium (Rs = 0.898), while the correlation between Hg(II) in MB and meconium was positive, but not significant. Maternal seafood intake was significantly correlated with meconium MeHg (Rs = 0.498) and Hg(II) (Rs = 0.201). Multiple linear regression (performed on the Slovenian population, N = 143) confirmed a positive association between meconium MeHg and seafood intake. Furthermore, meconium Hg(II) was positively associated with the number of maternal dental amalgam fillings, but linear regression models did not confirm correlation between seafood intake and meconium Hg(II) levels. We assume that Hg0 released from maternal dental amalgam fillings and MeHg from seafood intake were both transported through the placental barrier and portioned between different foetal compartments including meconium. Weak correlation between maternal seafood intake and Hg(II) levels in meconium suggests that there is certain evidence of MeHg demethylation. However, because this correlation was not confirmed by the multiple regression, MeHg demethylation during prenatal life cannot be neither confirmed nor excluded. Further investigations at higher level of exposure are needed to confirm this observations. We can conclude that meconium is a suitable biomarker for MeHg and Hg0 exposure during pregnancy. However, comparability of the results reported in meconium in different studies is hindered by a lack of standardized sampling protocols, storage, and analysis.

A Unique Interactive Nanostructure Knitting based Passive Sampler Adsorbent for Monitoring of Hg2+ in Water.

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.

Mercury speciation in prenatal exposure in Slovenian and Croatian population - PHIME study.

In recent years, several studies have addressed the issue of prenatal exposure to methylmercury (MeHg); however, few have actually analysed MeHg blood concentrations. Our study population included mothers and their new-borns from Slovenia (central region; N = 584) and Croatia (coastal region; N = 234). We have measurements of total Hg (THg) and MeHg in maternal hair, maternal peripheral blood, and cord blood. Cord blood Hg concentrations were low to moderate (median THg = 1.84 ng/g and MeHg = 1.69 ng/g). The proportion of THg as MeHg (%MeHg) in maternal and cord blood varied between 4% and 100% (coefficient of variation, CV = 32%) and between 8% and 100% (CV = 20%), respectively. Our data shows that variability of %MeHg was higher at lower blood THg levels. Concentrations of MeHg in maternal blood and cord blood were highly correlated (Rs = 0.943), in the case of inorganic Hg correlation was significant but weaker (Rs = 0.198). MeHg levels in maternal blood and cord blood were positively associated with seafood intake, maternal age, and negatively associated with pre-pregnancy BMI. Additionally, MeHg in maternal blood was positively associated with plasma selenium levels, and cord blood MeHg was negatively associated with parity. The results of multiple linear regression models showed that speciation analysis provides more defined estimation of prenatal exposure in association modelling. Associations between Hg exposure and cognitive performance of children (assessed using Bayley Scales of Infant and Toddler development) adjusted for maternal or child Apolipoprotein E genotypes showed higher model R2 and lower p-values when adjusted for MeHg compared to THg. This study demonstrates that Hg speciation improves the association between exposure and possible negative health effects.

Results of the first national human biomonitoring in Slovenia: Trace elements in men and lactating women, predictors of exposure and reference values.

The first national human biomonitoring in Slovenia surveyed cadmium (Cd), lead (Pb), mercury (Hg), arsenic (As), manganese (Mn), selenium (Se), copper (Cu) and zinc (Zn) in a childbearing population (18-49 years) selected from lactating primiparous women and men (N = 1084). The overall aim was to estimate trace elements' levels and geographical variations in order to identify sources of possible exposures and set the national reference values. The study population was selected evenly from 12 study areas across Slovenia, including rural, urban and known or potentially contaminated environments. Within 6-8 weeks after delivery, venous blood, spot urine, scalp hair and breast milk samples were collected to determine the selected elements. The data analysis included descriptive statistics and multiple linear regression using elemental concentrations in biological matrices, questionnaire data and environmental datasets. Essential elements showed no significant deficiencies or excessive levels in the study population and were largely determined by sex and/or the participating women's physiological status (postpartum, lactation), as well as by certain dietary sources. Toxic elements' levels were mainly below the levels considered to present increased health risk. Lifestyle and nutritional habits appeared as significant determinants of exposure to Cd (smoking and game meat consumption), Hg (seafood and amalgam fillings), As (seafood) and Pb (alcohol consumption, smoking, game meat consumption and type of water supply). A distinctive geographical pattern was confirmed, due to past mining activities combined with naturally elevated background levels in the cases of Pb (Mezica Valley), Hg (Idrija and Posocje) and As exposure (Zasavje). Increased seafood consumption in the coastal study area contributed to higher Hg and As (arsenobetaine) levels. Extensive sample size database accompanied with life-style and environmental data improved the prediction of exposure patterns, set the reference values for the childbearing population living in Slovenia, and provided a strong basis for evaluating spatial and temporal trends in exposure. To our best knowledge, this is the first study to establish reference values for lactating primiparous women.

Relations between mercury fractions and microbial community components in seawater under the presence and absence of probable phosphorus limitation conditions.

Microbial transformations of toxic monomethylmercury (MMHg) and dissolved gaseous mercury (DGM) at the lower levels of the marine food web are not well understood, especially in oligotrophic and phosphorus-limited seas. To examine the effects of probable phosphorus limitation (PP-limitation) on relations between mercury (Hg) fractions and microorganisms, we determined the total mercury (THg), total methylated mercury (MeHg), DGM, and microbiological and chemical parameters in the Central Adriatic Sea. Using statistical analysis, we assessed the potential microbial effects on Hg transformations and bioaccumulation. Only in the absence of PP-limitation conditions (NO-PP-limitation) is MeHg significantly related to most chemical and microbial parameters, indicating metabolism-dependent Hg transformations. The heterotrophic activity of low nucleic acid bacteria (abundant in oligotrophic regions) seems responsible for most of Hg methylation under NO-PP-limitation. Under these conditions, DGM is strongly related to microbial fractions and chlorophyll a, indicating biological DGM production, which is probably not metabolically induced, as most of these relations are also observed under PP-limitation. MMHg biomagnification was observed through an increased bioaccumulation factor from microseston to mesozooplankton. Our results indicate that Hg transformations and uptake might be enhanced under NO-PP-limitation conditions, emphasizing their impact on the transfer of Hg to higher trophic levels.

Bioaccumulation of As, Hg, and Se in tunas Thunnus albacares and Katsuwonus pelamis from the Eastern Pacific: tissue distribution and As speciation.

With the aim of knowing the distribution of As, Hg, and Se in skipjack (Katsuwonus pelamis, Linnaeus, 1758) and yellowfin tuna (Thunnus albacares, Bonnaterre, 1788) from the Eastern Pacific, elemental concentrations were determined in the muscle and liver; As species were also analyzed in the stomach content. Additionally, health risk for consumers was assessed. For both tunas, levels of As and Se were significantly higher (p < 0.05) in the liver than in the muscle. In K. pelamis, Hg concentrations in the muscle were significantly higher (p < 0.05) than those in the liver. In T. albacares, As, Hg, and Se showed a trend to increase with fish dimensions. Arsenic extractability was better in the muscle than in the liver of both species; in K. pelamis, As species were better extracted than in T. albacares. In both tuna species, the most extractable arsenic was arsenobetaine (AsB) and a minor part was dimethylarsinic acid (DMA). The liver contained mainly AsB with some DMA and arsenocholine (AsC). Hazard indexes (HI) indicated no risk from Hg and Se intake through these tuna species. Considering the individual contribution to the HI, Hg contributed more (80 to 86%) than Se. In the context of health risk, none of the As and Hg values were above the permissible limits; however, two samples of T. albacares (9%) and three samples of K. pelamis (12%) had Se concentrations over the limits. If Hg and Se in the edible portion of tuna are considered under the approach of the HBVSe, tuna consumption is beneficial.

Mercury in a stream-lake network of Andean Patagonia (Southern Volcanic Zone): Partitioning and interaction with dissolved organic matter.

Lake Nahuel Huapi (NH) is a large, ultraoligotrophic deep system located in Nahuel Huapi National Park (NHNP) and collecting a major headwater network of Northwestern Patagonia (Argentina). Brazo Rincón (BR), the westernmost branch of NH, is close to the active volcanic formation Puyehue-Cordón Caulle. In BR, aquatic biota and sediments display high levels of total Hg (THg), ranging in contamination levels although it is an unpolluted region. In this survey, Hg species and fractionation were assessed in association with dissolved organic matter (DOM) in several aquatic systems draining to BR. THg varied between 16.8 and 363 ng L-1, with inorganic Hg (Hg2+) contributing up to 99.8% and methyl mercury (MeHg) up to 2.10%. DOC levels were low (0.31-1.02 mg L-1) resulting in high THg:DOC and reflecting in high Hg2+ availability for binding particles (partitioning coefficient log Kd up to 6.03). In streams, Hg fractionation and speciation related directly with DOM terrestrial prints, indicating coupled Hg-DOM inputs from the catchment. In the lake, DOM quality and photochemical and biological processing drive Hg fractionation, speciation and vertical levels. Dissolved gaseous Hg (Hg0) reached higher values in BR (up to 3.8%), particularly in upper lake layers where solar radiation enhances the photoreduction of Hg2+ and Hg-DOM complexes. The environmental conditions in BR catchment promote Hg2+ binding to abiotic particles and bioaccumulation and the production of Hg0, features enhancing Hg mobilization among ecosystem compartments. Overall, the aquatic network studied can be considered a "natural Hg hotspot" within NHNP.

Species- and habitat-specific bioaccumulation of total mercury and methylmercury in the food web of a deep oligotrophic lake.

Niche segregation between introduced and native fish in Lake Nahuel Huapi, a deep oligotrophic lake in Northwest Patagonia (Argentina), occurs through the consumption of different prey. Therefore, in this work we analyzed total mercury [THg] and methylmercury [MeHg] concentrations in top predator fish and in their main prey to test whether their feeding habits influence [Hg]. Results indicate that [THg] and [MeHg] varied by foraging habitat and they increased with greater percentage of benthic diet and decreased with pelagic diet in Lake Nahuel Huapi. This is consistent with the fact that the native creole perch, a mostly benthivorous feeder, which shares the highest trophic level of the food web with introduced salmonids, had higher [THg] and [MeHg] than the more pelagic feeder rainbow trout and bentho-pelagic feeder brown trout. This differential THg and MeHg bioaccumulation observed in native and introduced fish provides evidence to the hypothesis that there are two main Hg transfer pathways from the base of the food web to top predators: a pelagic pathway where Hg is transferred from water, through plankton (with Hg in inorganic species mostly), forage fish to salmonids, and a benthic pathway, as Hg is transferred from the sediments (where Hg methylation occurs mostly), through crayfish (with higher [MeHg] than plankton), to native fish, leading to one fold higher [Hg].

The dynamics of mercury near Idrija mercury mine, Slovenia: Horizontal and vertical distributions of total, methyl, and ethyl mercury concentrations in soils.

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.

An inter-laboratory comparison of different analytical methods for the determination of monomethylmercury in various soil and sediment samples: A platform for method improvement.

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.

Prenatal mercury exposure, neurodevelopment and apolipoprotein E genetic polymorphism.

The aim of the present study was to evaluate the association between prenatal exposure to mercury (Hg) and neurodevelopment of the child, taking into account genetic polymorphism of apolipoprotein E (Apoe) and other relevant confounders. Six hundred and one mother-child pairs were recruited from the central Slovenia region and 243 from Rijeka, on the Croatian coast of the northern Adriatic. The total Hg in cord blood, Bayley Scales of Infant and Toddler Development, Third Edition (Bayley-III) assessment at 18 months of age and Apoe genotyping was performed on 361 children; 237 of them were from Slovenia and 124 from Croatia. The results showed negative association between low-to-moderate Hg exposure in children with normal neurodevelopmental outcome and cognitive and fine motor scores at 18 months of age as assessed by Bayley III. The Hg-related decrease in cognitive score was observed only in children carrying at least one Apoe ε4 allele, while the decrease in fine motor scores was independent of the Apoe genotype. Adjusting for selenium (Se) and lead (Pb) levels, a positive association between Se and the language score and a negative association between Pb and the motor score was observed, but not in the subgroup of children carrying the ε4 allele.

Exposure to mercury in susceptible population groups living in the former mercury mining town of Idrija, Slovenia.

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.

Biogeochemical, Isotopic and Bacterial Distributions Trace Oceanic Abyssal Circulation.

We explore the possibility of tracing routes of dense waters toward and within the ocean abyss by the use of an extended set of observed physical and biochemical parameters. To this purpose, we employ mercury, isotopic oxygen, biopolymeric carbon and its constituents, together with indicators of microbial activity and bacterial diversity found in bottom waters of the Eastern Mediterranean. In this basin, which has been considered as a miniature global ocean, two competing sources of bottom water (one in the Adriatic and one in the Aegean seas) contribute to the ventilation of the local abyss. However, due to a recent substantial reduction of the differences in the physical characteristics of these two water masses it has become increasingly complex a water classification using the traditional approach with temperature, salinity and dissolved oxygen alone. Here, we show that an extended set of observed physical and biochemical parameters allows recognizing the existence of two different abyssal routes from the Adriatic source and one abyssal route from the Aegean source despite temperature and salinity of such two competing sources of abyssal water being virtually indistinguishable. Moreover, as the near-bottom development of exogenous bacterial communities transported by convectively-generated water masses in the abyss can provide a persistent trace of episodic events, intermittent flows like those generating abyssal waters in the Eastern Mediterranean basin may become detectable beyond the availability of concomitant measurements.

Mercury speciation in the Adriatic Sea.

Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM ­ dissolved gaseous Hg, RHg ­ reactive Hg, THg ­ total Hg, MeHg ­ monomethyl Hg and DMeHg ­ dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data.

Speciation of methyl- and ethyl-mercury in hair of breastfed infants acutely exposed to thimerosal-containing vaccines.

BACKGROUND: 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. METHODS: The hair of infants (<12 months) 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. RESULTS: In 20 samples of infants' hair, all but two samples showed variable amounts of MeHg (10.3 to 668 ng/g), while precise and reliable concentrations of EtHg (3.7 to 65.0 ng/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. CONCLUSIONS: 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.

[Fetal and perinatal exposure to mercury and selenium: baseline evaluation of a cohort of children in Friuli Venezia Giulia, Italy]. / Esposizione fetale e perinatale a mercurio e selenio: valutazione alla baseline di una coorte di bambini del Friuli Venezia Giulia.

OBJECTIVE: neurotoxicity of prenatal exposure to high concentrations of mercury (Hg) is well known; however, the doseresponse relationship at low exposure levels has not been quantified yet. This article illustrates the measurement of prenatal exposure to Hg and the pathway of exposure through the diet in Friuli Venezia Giulia, Italy. DESIGN: description of a prospective cohort at the baseline. SETTING AND PARTICIPANTS: 242 mother- infant pairs living in Friuli Venezia Giulia were enrolled between 1999 and 2001. MAIN OUTCOME MEASURES: We measured the concentrations of Hg in the hair of mothers and children and of Hg and selenium (Se) in breast milk. The diet during pregnancy was estimated through a food frequency questionnaire (FFQ) with a detailed section regarding fish. We calculated the correlations between Hg and Se in the biological samples and estimated the association between Hg concentrations and fish consumption. RESULTS: in general, Hg levels in hair and milk were positively associated with the consumption of fish from the lagoon of Grado and Marano. However, they were low in comparison with those of other fish-eating populations and below theWHO alert limits, likely because of the small consumption of fish among pregnant women, estimated from the FFQ. The concentration of Se in milk was also smaller than that reported in other international studies. CONCLUSION: in Friuli Venezia Giulia, fetal and perinatal Hg exposure is low. The children of the cohort will be followed- up at school age to measure possible neurodevelopmental effects of such low exposures to Hg.

Biomonitoring with epiphytic lichens as a complementary method for the study of mercury contamination near a cement plant.

The study was focused on understanding the mercury contamination caused by a cement plant. Active and passive biomonitoring with epiphytic lichens was combined with other instrumental measurements of mercury emissions, mercury concentrations in raw materials, elemental mercury concentrations in air, quantities of dust deposits, temperatures, precipitation and other measurements from the cement plant's regular monitoring programme. Active biomonitoring with transplanted lichens Pseudevernia furfuracea (L.) Zopf was performed at seven of the most representative sites around the cement plant and one distant reference site for periods of 3, 6 and 12 months. In situ lichens of different species were collected at the beginning of the monitoring period at the same sites. Mercury speciation of the plant exhaust gas showed that the main form of emitted mercury is reactive gaseous mercury Hg²âº, which is specific for cement plants. Elemental mercury in air was measured in different meteorological conditions using a portable mercury detector. Concentrations in air were relatively low (on average below 10 ng m⁻³). In situ lichens showed Hg concentrations comparable to lichens taken from the background area for transplantation, indicating that the local pollution is not severe. Transplanted lichens showed an increase of mercury, especially at one site near the cement plant. A correlation between precipitation and Hg uptake was not found probably due to a rather uniform rainfall in individual periods. Dust deposits did not influence Hg uptake significantly. Lichens vitality was affected over longer biomonitoring periods, probably due to some elements in dust particles, their alkalinity and the influence of other emissions. Mercury uptake measured in vital transplanted lichens was in a good correlation with the working hours (i.e. emitted Hg quantity) of the kiln. The study showed that selected lichens could be used to detect low to moderate Hg emissions from a cement plant and that the biomonitoring procedure could be further standardized and used as part of an environmental monitoring programme.