Single-cell ICP-MS for evaluating the Se-protective effect against MeHg+-induced neurotoxicity in human neuroblastoma cell line (SH-SY5Y).

The protective effect of selenium (Se) against Hg-induced neurotoxicity has been widely investigated; however, the mechanisms behind this interaction have not been fully elucidated yet. In the current work, the role of Se against MeHg+-induced cytotoxicity in the human neuroblastoma cell line (SH-SY5Y) is reported for the first time by tracking Hg uptake and accumulation at the single-cell level by inductively coupled plasma-mass spectrometry in single-cell mode (SC-ICP-MS). The influence of different Se species (SeMet, SeMeSeCys, citrate-SeNPs, and chitosan-SeNPs) on MeHg+ cytotoxicity was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays. SeMet and SeMeSeCys exhibited protective effects against MeHg+-induced cell death, particularly at high MeHg+ concentrations (LC50). In addition, chitosan-SeNPs showed greater protection compared to citrate-SeNPs when co-exposed with MeHg+. Interestingly, SC-ICP-MS unveiled the heterogeneous distribution of Hg uptake by SH-SY5Y cells. Co-exposure of SeMet and SeMeSeCys with MeHg+ led to a reduction of the amount of Hg accumulated per individual cell, which decreased the maximum level of Hg per cell by half (from 60 fg Hg cell-1 to 30 fg Hg cell-1) when SeMet was present, along with a decrease in the percentage of cells that accumulated the highest quantity of MeHg+. All these data corroborate the protective role of Se against Hg toxicity at the cellular level.

An improved method for rapid and safe preparation and measurement of dimethylmercury using gas chromatography-atomic fluorescence spectrometry.

Transformations between dimethylmercury (DMHg) and other mercury (Hg) species have been one of the critical knowledge gaps in the Hg global biogeochemical cycle due to the lack of detailed studies. The preparation and measurement of DMHg are challenging due to the high toxicity and volatility of DMHg. In this work, we invented a new DMHg generator for successfully preparing high-purity DMHg in a highly controllable and safe way. The DMHg could be spontaneously volatilized and diffused from the original preparation solution to the solution to be studied. The parameters for generating DMHg were optimized to be the pH value of 4.0 with a MeCo/Hg2+ molar ratio of 10 at 20 °C. The following measurement method of DMHg in the presence of various species of Hg was also investigated and optimized. Hg0 and DMHg could be separated effectively with the carrier gas flow rate of 15 mL min-1 and the gas chromatography column temperature of 30 °C. The interferences of Hg0, monomethylmercury and other species were excluded by systematic control experiments. A sensitive and reliable approach for quantifying trace DMHg in water was developed. Under the optimal conditions, the limits of detection for Hg0, MMHg and DMHg were 0.03, 0.002 and 0.024 ng L-1, respectively, with the relative standard deviation below 8.2%. The developed method was validated by the determination Hg species of different natural water samples. This work is expected to provide a new and safe strategy for DMHg preparation and a verified method for DMHg measurement.

Elevated methylmercury production in mercury-contaminated paddy soil resulted from the favorable dissolved organic matter variation created by algal decomposition.

Algae-derived organic matter (AOM) may considerably regulate methylmercury (MeHg) production and accumulation in the paddy fields by changing the soil-dissolved OM (SDOM) properties. In this study, a 25-day microcosm experiment was performed to compare the responding mechanisms of MeHg production in the Hg-contaminated paddy soil-water system to the input of algae-, rice-, and rape-derived OMs. Results showed that algal decomposition could release much more cysteine and sulfate than crop straws. Compared with crop straw-derived OMs, AOM input greatly increased the dissolved organic carbon concentrations in soil but resulted in a greater decrease in tryptophan-like fractions while accelerated the formation of high-molecular-weight fractions in soil DOM. Moreover, AOM input significantly increased MeHg concentrations in the pore water by 19.43%-3427.66% and 52.81%-5846.57% compared to rape- and rice-derived OMs, respectively (P < 0.05). And, a similar MeHg changing pattern was also observed in the overlying water (10-25 d) and the soil solid-phase particles (15-25 d) (P < 0.05). Correlation analysis revealed that MeHg concentrations in the AOM-added soil-water system had significantly negative and positive relationships with the tryptophan-like C4 fraction and molecular weight (E2/E3 ratio) of soil DOM, respectively (P < 0.01). These findings suggest that AOM has a higher capacity than crop straw-derived OMs to promote MeHg production and accumulation in the Hg-contaminated paddy soils by creating a favorable soil DOM variation and providing more microbial electron donors and receptors.

Risk assessment of mercury through dietary exposure in China.

Mercury (Hg) is a widespread heavy metal causing various damages to health, while insufficient studies assessed its exposure risk across China. This study explored concentrations in food items and dietary exposure risks across China by comprehensively analyzing the researches on total Hg (THg) in eight food items and methylmercury (MeHg) in aquatic foods published between 1980 and 2021. According to the included 695 studies, the average THg concentration in all food items was 0.033 mg/kg (ranging from 0.004 to 0.185 mg/kg), with the highest concentration in edible fungi. The average daily dietary THg exposure from all foods was 12.9 µg/day. Plant-based foods accounted for 62.7% of the dietary THg exposure. Cereals and vegetables were the primary source of THg exposure. The MeHg concentration in aquatic foods was 0.08 mg/kg, and the average dietary exposure was 3.8 µg/day. Monte Carlo simulations of the dietary exposure risk assessment of THg and MeHg showed that approximately 6.4 and 7.0% of residents exceeded the health-based guidance value set by the European Food Safety Authority, with higher exposure risk in Southwest and South China. The nationwide target hazard quotient index of THg was greater than 1, suggesting that the non-carcinogenic risk of dietary exposure to THg needed further concern. In summary, this study has a comprehensive understanding of dietary Hg exposure risks across China, which provide a data basis for Hg exposure risk assessment and policy formulation.

Health risk assessment for human exposure to mercury species and arsenic via consumption of local food in a gold mining area in Colombia.

The risk to human health from exposure to certain pollutants through the consumption of fruits, tubers, and fish were evaluated in a settlement located in a Colombian area highly impacted by gold mining activities. The concentrations of mercury (Hg) and arsenic (As) in edible food tissues and methylmercury (MeHg) in fish were determined for risk assessment. A questionnaire-based dietary survey was answered by 178 residents of three population groups: children (CHD), women of childbearing age (WCBA), and the rest of the population (RP). The estimated weekly intake (EWI) of MeHg presented values of 1.9 and 2.4 times higher than the provisional tolerable weekly intake (1.6 µg/kg BW/week) recommended by the FAO/WHO for CH and WCBA, respectively. The results of the HQ values of As and Hg for different food were above the safety level (HQ < 1) for most of the groups. For Hg, the highest HQ values correspond to fish, whereas for As in most of the food, but specially in fruits. The total target hazard quotients (HI) were higher than 1, in all the groups (except for CHD that consume tubers) indicating potential non-carcinogenic health risks. The values of carcinogenic risk (CR) for As through exposure to food ranged from 1.2·10-4 to 7.7·10-4, well above than the safety level of US EPA risk (10-4-10-6), suggesting the probability of carcinogenic risk for the entire population via ingestion. Therefore, safety control mechanisms and environmental education strategies should be applied to address food intake, associated with good agricultural practices to provide solutions to protect the health of the residents in areas affected by gold mining activities.

Important Roles of Thiols in Methylmercury Uptake and Translocation by Rice Plants.

The bioaccumulation of the neurotoxin methylmercury (MeHg) in rice is a significant concern due to its potential risk to humans. Thiols have been known to affect MeHg bioavailability in microorganisms, but how thiols influence MeHg accumulation in rice plants remains unknown. Here, we investigated effects of common low-molecular-weight thiols, including cysteine (Cys), glutathione (GSH), and penicillamine (PEN), on MeHg uptake and translocation by rice plants. Results show that rice roots can rapidly take up MeHg, and this process is influenced by the types and concentrations of thiols in the system. The presence of Cys facilitated MeHg uptake by roots and translocation to shoots, while GSH could only promote MeHg uptake, but not translocation, by roots. Conversely, PEN significantly inhibited MeHg uptake and translocation to shoots. Using labeled 13Cys assays, we also found that MeHg uptake was coupled with Cys accumulation in rice roots. Moreover, analyses of comparative transcriptomics revealed that key genes associated with metallothionein and SULTR transporter families may be involved in MeHg uptake. These findings provide new insights into the uptake and translocation of MeHg in rice plants and suggest potential roles of thiol attributes in affecting MeHg bioavailability and bioaccumulation in rice.

A human health risk assessment of methylmercury, arsenic and metals in a tropical river basin impacted by gold mining in the Colombian Pacific region.

The Atrato River basin is one of the most biodiverse areas worldwide, and paradoxically, it is one of the sites in Colombia with the highest environmental impact from gold mining. This study assessed the distribution of Hg, As, Pb, and Cd in 47 fish species (n = 1372) and the accumulative human health risk in inhabitants (n = 2325) from 13 municipalities located along the Atrato River basin. The results revealed that Hg and As in fish present a high potential human health risk based on their mean concentrations. Estimated daily intake (EDI) calculations showed that humans could present detrimental health effects, while that target hazard quotient (THQ) above 1 showed that the exposed population might experience noncarcinogenic health risks, mainly from the accumulative effects of Hg (80.4%) and As (18.2%). The species that would most affect the health of the inhabitants are carnivorous H. malabaricus, A. pardalis, P. schultzi, R. quelen, and C. kraussii, which are among the fourteen most consumed in the region. These species had values of estimated weekly intake (EWI) above the provisional tolerable weekly intake thresholds for MeHg (PTWI of 1.6 and 3.2 µg/kg bw/week for adults and children, respectively) in 7 of the 13 localities evaluated. According to the surveys, the calculated weekly allowable fish amount (MFW) showed that carnivorous fish may generate adverse effects on the consumers because the allowed MeHg is about 2 times higher than the upper reference limit. Other results indicate a significant carcinogenic health risk, mainly from As, in 8 of the 13 localities evaluated. Due to the high rates of unsatisfied basic needs and the monetary poverty in the region, the possibility that inhabitants can replace fish as the principal source of protein is low. Therefore, a food guidance is required to avoid risks, obtain nutritional benefits, and sustain fish populations.

Distribution and accumulation of mercury in pot-grown African rice cultivars (Oryza glaberrima Steud. and Oryza sativa L.) determined via LA-ICP-MS.

There is limited information concerning the distribution of mercury in rice, particularly in African rice. The objective was to compare the distribution of total mercury (THg) and methylmercury (MeHg) in African rice (Oryza glaberrima Steud.) and Asian rice (O. sativa L.). It is hypothesized that increased mineral accumulation and greater stress tolerance in O. glaberrima will affect the uptake and distribution of THg and MeHg, compared to O. sativa. Rice varieties from the Republic of Mali, including O. glaberrima (n =1) and O. sativa (n = 2), were cultivated in a greenhouse, in mercury-spiked soil (50 mg/kg) (n =3 replicates/variety). THg and MeHg concentrations were analyzed in the grain (brown rice), and the THg distribution was analyzed using laser ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS). THg and MeHg concentrations did not differ between O. glaberrima and O. sativa grain. However, in both O. sativa varieties, THg was highly concentrated in the scutellum, which surrounds the embryo and is removed during polishing. Conversely, in O. glaberrima grain, THg was widely distributed throughout the endosperm, the edible portion of the grain. Differences in the THg distribution in O. glaberrima grain, compared to O. sativa, may elevate the risk of mercury exposure through ingestion of polished rice. The novelty of this study includes the investigation of a less-studied rice species (O. glaberrima), the use of a highly sensitive elemental imaging technique (LA-ICP-MS), and its finding of a different grain THg distribution in O. glaberrima than has been observed in O. sativa.

Amino Acid Transporter LAT1 (SLC7A5) Mediates MeHg-Induced Oxidative Stress Defense in the Human Placental Cell Line HTR-8/SVneo.

The placental barrier can protect the fetus from contact with harmful substances. The potent neurotoxin methylmercury (MeHg), however, is very efficiently transported across the placenta. Our previous data suggested that L-type amino acid transporter (LAT)1 is involved in placental MeHg uptake, accepting MeHg-L-cysteine conjugates as substrate due to structural similarity to methionine. The aim of the present study was to investigate the antioxidant defense of placental cells to MeHg exposure and the role of LAT1 in this response. When trophoblast-derived HTR-8/SVneo cells were LAT1 depleted by siRNA-mediated knockdown, they accumulated less MeHg. However, they were more susceptible to MeHg-induced toxicity. This was evidenced in decreased cell viability at a usually noncytotoxic concentration of 0.03 µM MeHg (~6 µg/L). Treatment with ≥0.3 µM MeHg increased cytotoxicity, apoptosis rate, and oxidative stress of HTR-8/SVneo cells. These effects were enhanced under LAT1 knockdown. Reduced cell number was seen when MeHg-exposed cells were cultured in medium low in cysteine, a constituent of the tripeptide glutathione (GSH). Because LAT1-deficient HTR-8/SVneo cells have lower GSH levels than control cells (independent of MeHg treatment), we conclude that LAT1 is essential for de novo synthesis of GSH, required to counteract oxidative stress. Genetic predisposition to decreased LAT1 function combined with MeHg exposure could increase the risk of placental damage.

Association between genetic variations in GSH-related and MT genes and low-dose methylmercury exposure in children and women of childbearing age: a pilot study.

BACKGROUND: Genetic variations in glutathione (GSH)-related and metallothionein (MT) genes, which are involved in producing enzymes in the methylmercury (MeHg) metabolism pathway, have been proposed as one of the reasons for the individual variability in MeHg toxicokinetics. OBJECTIVE: To investigate the impact of genetic variations in MT and GSH-related genes on the association of fish consumption with body burden of MeHg, as measured by hair Hg concentrations among young children and women of childbearing age. METHODS: A total of 179 unrelated children and 165 mothers with either high or low fish consumption were recruited from the community. Their hair total Hg (tHg) and MeHg levels and genotypes for SNPs located on the GCLC, GCLM, GPX1, GSTA1, GSTP1, MT1A, MT2A, and MT4 genes were determined. Based on their 14-day food records, the amounts of fish consumed and their MeHg intakes were estimated. The impact of genetic variations on hair Hg concentrations was examined by using Mann-Whitney tests and multivariable linear regression analyses. RESULTS: The presence of minor alleles of GCLC-129 (rs17883901), GPX1-198 (rs1050450) and MT1M (rs9936741) were associated with significantly lower hair tHg levels in mothers whereas mothers with minor alleles of GSTP1-105(rs1695) and MT1M (rs2270836) have significantly higher hair tHg levels. After adjustment for fish consumption and other confounding factors, apart from MT1M (rs2270836), all of the above SNPs remain significant in the multivariable linear regression models. CONCLUSIONS: Our results in a group of children and women show that genetic variants of GSH-related and MT genes are associated with hair Hg concentrations. These genetic variations are likely to significantly affect MeHg metabolism and thus influence the accumulation of Hg in the human body.

Mitigation of mercury accumulation in rice using rice hull-derived biochar as soil amendment: A field investigation.

Effect of application of 24 t ha-1 and 72 t ha-1 rice hull-derived biochar (RHB) on total Hg (THg) and methylHg (MeHg) immobilization and their accumulations by rice plants were studied in a field experiment (Wanshan Hg mine, China). The addition of two doses of RHB significantly increased the biomass of rice plants, and decreased the MeHg concentration in the pore water, as compared to the control. The RHB promoted the partitioning of pore water MeHg to the soil solid phase throughout rice growing season, and pore water THg partitioning only at rice filling stage. Mercury methylation potential was weakly affected by the RHB addition to the soil. Mercury might be immobilized through binding of thiols (e.g., cysteine) presented in the RHB or in the soil induced by RHB addition. Biochar addition decreased MeHg and THg contents in the tissues of rice plants, particularly in the polished rice. We attributed the reduction of THg in the rice to the bio-dilution effect, and of MeHg content in the rice to the decreased MeHg availability in the soil by RHB addition. Results suggest that RHB might be suitable for managing Hg transfer in soil-rice plants at Hg contaminated mining regions in China and beyond.

Sensitive determination of methylmercury δ13C compound specific stable isotopic analysis by purge and trap gas chromatography combustion isotope ratio mass spectrometry.

Despite several decades of mercury research, answering fundamental questions on where and how methylmercury (CH3Hg) toxin is naturally produced in aquatic ecosystems, is still highly challenging. Investigating complex and/or coupled processes in the context of global changes requires new high-resolution analytical tools. The purpose of the compound specific carbon stable isotopic analysis (δ13C-CSIA) of the methyl group of methylmercury (CH3Hg), is to explore how the carbon cycle contributes to CH3Hg sources and formation pathways. The main problem associated with recent CH3Hg δ13C-CSIA methods is the limited sensitivity when using Liquid Injection (LI)-GC-C-IRMS techniques, requiring several micrograms of CH3Hg (as Hg). In this work, we present the development and application of an original Purge-&-Trap system (PT) coupled to a GC-C-IRMS with the purpose of transferring and analyzing the total amount of CH3Hg available in a sample vial in the low nanogram range. The new PT-GC-C-IRMS system enhance the sensitivity by a factor better than 200, relative to LI-GC-C-IRMS, by minimizing the sample mass requirements. The δ13CCH3Hg values obtained, following the same sample derivatization approach coupled to PT-GC-C-IRMS (-53.5 ± 1.9 ‰), were in good agreement with the ones obtained in a previous study (-53.8 ± 1.1 ‰). The standard solution was prepared from the same salt, requesting only 25-200 ng of CH3Hg (as Hg). This new methodology represents a milestone towards the analysis of large array of biological samples displaying CH3Hg concentrations in the low-mid ng g-1 range, in order to explore the meaning of the carbon stable isotopic signature of CH3Hg in the environment.

Determination of picomolar levels of methylmercury complexes with low molecular mass thiols by liquid chromatography tandem mass spectrometry and online preconcentration.

Methylmercury (MeHg) is one of the most potent neurotoxins. It is produced in nature through the methylation of inorganic divalent mercury (HgII) by phylogenetically diverse anaerobic microbes. The mechanistic understanding of the processes that govern the extent of bacterial export of MeHg, its bioaccumulation, and bio-toxicity depends on accurate quantification of its species, especially its complexation with low molecular mass thiols; organometallic complexes that are difficult to detect and measure in natural conditions. Here, we report the development of a novel analytical method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) to determine 13 MeHg complexes with important thiol compounds which have been observed in the environment and in biological systems. By using online preconcentration via solid phase extraction (SPE), the method offers picomolar (12-530 pM) detection limits, the lowest reported so far for the determination of MeHg compounds. Among three different SPE materials, a weak cation exchange phase showed the best efficiency at a low pH of 2.5. We further report the presence of MeHg-cysteine, MeHg-cysteamine, MeHg-penicillamine, MeHg-cysteinylglycine, and MeHg-glutamylcysteine as the predominant MeHg-thiol complexes in the extracellular milieu of an important HgII methylating bacterium, Geobacter sulfurreducens PCA, exposed to 100 nM of HgII.

Health effects of nutrients and environmental pollutants in Baltic herring and salmon: a quantitative benefit-risk assessment.

BACKGROUND: Health risks linked with dioxin in fish remain a complex policy issue. Fatty Baltic fish contain persistent pollutants, but they are otherwise healthy food. We studied the health benefits and risks associated with Baltic herring and salmon in four countries to identify critical uncertainties and to facilitate an evidence-based discussion. METHODS: We performed an online survey investigating consumers' fish consumption and its motivation in Denmark, Estonia, Finland, and Sweden. Dioxin and methylmercury concentrations were estimated based on Finnish studies. Exposure-response functions for several health endpoints were evaluated and quantified based on the scientific literature. We also quantified the infertility risk of men based on a recent European risk assessment estimating childhood dioxin exposure and its effect on sperm concentration later in life. RESULTS: Baltic herring and salmon contain omega-3 fatty acids and vitamin D, and the beneficial impact of these fishes on cardiovascular diseases, mortality, and the risk of depression and cancer clearly outweighs risks of dioxins and methylmercury in people older than 45 years of age and in young men. Young women may expose their children to pollutants during pregnancy and breast feeding. This study suggests that even in this critical subgroup, the risks are small and the health benefits are greater than or at least similar to the health risks. Value of information analysis demonstrated that the remaining scientific uncertainties are not large. In contrast, there are several critical uncertainties that are inherently value judgements, such as whether exceeding the tolerable weekly intake is an adverse outcome as such; and whether or not subgroup-specific restrictions are problematic. CONCLUSIONS: The potential health risks attributable to dioxins in Baltic fish have more than halved in the past 10 years. The new risk assessment issued by the European Food Safety Authority clearly increases the fraction of the population exceeding the tolerable dioxin intake, but nonetheless, quantitative estimates of net health impacts change only marginally. Increased use of small herring (which have less pollutants) is a no-regret option. A more relevant value-based policy discussion rather than research is needed to clarify official recommendations related to dioxins in fish.

Does the addition of ingredients affect mercury and cadmium bioaccessibility in seafood-based meals?

Despite the bioaccessibility of nutrients and contaminants present in individual seafood products has been thoroughly studied, information is extremely limited in what concerns complete seafood-based meals, where interactions between ingredients may occur. Hence, this study aimed to evaluate the effect of different ingredients and cooking processes in mercury (Hg) and cadmium (Cd) bioaccessibility in complete meals of tuna (Thunnus spp.) and edible crab (Cancer pagurus), respectively. The addition of ingredients/side dishes decreased Hg levels in cooked tuna meals, but increased Hg bioaccessibility (up to 31% of bioaccessible Hg in complete meals, against 13.5% in stewed tuna alone). Cd levels in edible crab meals were significantly decreased by the addition of ingredients (~36% and ~65% decrease in boiled crab and paté, respectively), but its' bioaccessibility was not significantly affected (>94% in all cases). Results showed that the weekly consumption of 2 complete tuna meals does not exceed MeHg tolerable weekly intake (TWI), whereas Cd's TWI is largely surpassed with the consumption of 50 g/week of edible crab meals. This highlights the importance of determining contaminant levels and bioaccessibility in a whole seafood-based meal context, as such approach enables a more realistic assessment of the risks that seafood can pose to consumers.

Development of a Novel Equilibrium Passive Sampling Device for Methylmercury in Sediment and Soil Porewaters.

We explored the concept of equilibrium passive sampling for methylmercury (MeHg) using the strategy developed for hydrophobic organic chemicals. Passive sampling should allow prediction of the concentration of the chemically labile fraction of MeHg in sediment porewaters based on equilibrium partitioning into the sampler, without modeling diffusion rates through the sampler material. Our goals were to identify sampler materials with the potential to mimic MeHg partitioning into animals and sediments and provide reversible sorption in a time frame appropriate for in situ samplers. Candidate materials tested included a range of polymers embedded with suitable sorbents for MeHg. The most promising were activated carbon (AC) embedded in agarose, thiol-self-assembled monolayers on mesoporous supports embedded in agarose, and cysteine-functionalized polyethylene terephthalate, which yielded log sampler-water partition coefficients of 2.8 to 5 for MeHgOH and MeHg complexed with dissolved organic matter (Suwannee River humic acid). Sampler equilibration time in sediments was approximately 1 to 2 wk. Investigation of the MeHg accumulation mechanism by AC embedded in agarose suggested that sampling was kinetically influenced by MeHg interactions with AC particles and not limited by diffusion through the gel for this material. Also, AC exhibited relatively rapid desorption of Hg and MeHg, indicating that this sorbent is capable of reversible, equilibrium measurements. In sediment:water microcosms, porewater concentrations made with isotherm-calibrated passive samplers agreed within a factor of 2 (unamended sediment) or 4 (AC-amended sediment) with directly measured concentrations. The present study demonstrates a potential new approach to passive sampling of MeHg. Environ Toxicol Chem 2020;39:323-334. © 2019 SETAC.

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.

The interaction of mercury and methylmercury with chalcogenide nanoparticles.

Mercury (Hg) and methylmercury (CH3Hg) bind strongly to micro and nano (NP) particles and this partitioning impacts their fate and bioaccumulation into food webs, and, as a result, potential human exposure. This partitioning has been shown to influence the bioavailability of inorganic Hg to methylating bacteria, with NP-bound Hg being more bioavailable than particulate HgS, or organic particulate-bound Hg. In this study we set out to investigate whether the potential interactions between dissolved ionic Hg (HgII) and CH3Hg and NPs was due to incorporation of Hg into the core of the cadmium selenide and sulfide (CdSe; CdS) nanoparticles (metal exchange or surface precipitation), or due purely to surface interactions. The interaction was assessed based on the quenching of the fluorescence intensity and lifetime observed during HgII or CH3Hg titration experiments of these NP solutions. Additional analysis using inductively coupled plasma mass spectrometry of CdSe NPs and the separated solution, obtained after HgII additions, showed that there was no metal exchange, and X-ray photoelectron spectroscopy confirmed this and further indicated that the Hg was bound to cysteine, the NP capping agent. Our study suggests that Hg and CH3Hg adsorbed to the surfaces of NPs would have different bioavailability for release into water or to (de)methylating organisms or for bioaccumulation, and provides insights into the behavior of Hg in the environment in the presence of natural or manufactured NPs.

Methylmercury exposure, genetic variation in metabolic enzymes, and the risk of glioma.

Methylmercury (MeHg) is an environmental neurotoxin with human exposure mainly from dietary intake of contaminated fish. Exposure to MeHg has been implicated in neurological damage, but research on its role in cancers, specifically glioma, is limited. In a glioma case-control study, we examined associations between toenail mercury (Hg) and glioma risk. We also examined genetic polymorphisms in 13 genes related to MeHg metabolism for association with glioma risk; genetic associations were also studied in the UK Biobank cohort. Median toenail Hg in cases and controls, respectively, was 0.066 µg/g and 0.069 µg/g (interquartile range (IQR): 0.032-0.161 and 0.031-0.150 µg/g). Toenail Hg was not found to be significantly associated with glioma risk (Odds Ratio: 1.02; 95% Confidence Interval: 0.91, 1.14; p = 0.70 in analysis for ordinal trend with increasing quartile of toenail MeHg). No genetic variant was statistically significant in both of the studies; one variant, rs11859163 (MMP2) had a combined p-value of 0.02 though it was no longer significant after adjustment for multiple testing (Bonferroni corrected p = 1). This study does not support the hypothesis that exposure to MeHg plays a role in the development of glioma at levels of exposure found in this study population.

Preliminary investigation of polymer-based in situ passive samplers for mercury and methylmercury.

Development of an in situ passive sampler for mercury (Hg), and its toxic form, methylmercury (MeHg), using simple polymer films, was explored for the potential to make an efficient and environmentally relevant monitoring tool for this widespread aquatic pollutant. The sulfur-containing polymers polysulfone (PS), and polyphenylene sulfide (PPS), were found to accumulate both MeHg and inorganic Hg (iHg), whereas polyethylene (PE) sorbed iHg but not MeHg, and polyoxymethylene (POM) and polyethersulfone (PES) films had low affinity for both Hg species. Uptake rates of Hg species into polymers were linear over two weeks, and dissolved organic matter at natural levels had no effect on partitioning of MeHg or iHg to the polymers. Sorption of MeHg to PS and PPS from three estuarine sediments correlated with uptake into diffusive gel-type samplers over time, and in PPS, with accumulation by the estuarine amphipod, Leptocheirus plumulosus. These polymers had lower MeHg adsorption rates, but are simpler to assemble, than diffusive gel-type samplers. Higher contaminant concentrations in polymer and gel-type samplers corresponded with porewater concentrations across sediments, suggesting they sample the dissolved MeHg pool, whereas MeHg levels in amphipods were more elevated with higher bulk sediment MeHg, which may reflect feeding strategy. While polymers with higher affinity for MeHg and iHg are needed for some environmental applications, this work suggests a simple sampling approach has potential for time-integrated, environmentally-meaningful MeHg monitoring in contaminated sediments.