Distribution and phylogeny of mercury methylation, demethylation, and reduction genes in the Seto Inland Sea of Japan.

Mercury (Hg) adversely affects human and environmental health. To evaluate the mercury (Hg) speciation (methylation, demethylation, and reduction) of microorganisms in coastal seawater, we analyzed the microbial functional gene sets involved in Hg methylation (hgcA and hgcB), demethylation (merB), and reduction (merA) using a metagenomic approach in the eastern and western parts (the Kii and Bungo channels, respectively) of the Seto Inland Sea (SIS) of Japan. We determined the concentration of dissolved total mercury (dTHg) and methylated mercury (dMeHg) in seawater. The metagenomic analysis detected hgcAB, merA, and merB in both channels, whereas the phylogenies of these genes differed between them. A correlation between Hg concentration (both dTHg and dMeHg) and the relative abundance of each gene was not observed. Our data suggests that microbial Hg methylation and demethylation could occur in the SIS and there could be a distinct microbial Hg speciation process between the Kii and Bungo channels.

Organ-specific accumulation of selenium and mercury in Indo-Pacific bottlenose dolphins (Tursiops aduncus).

Delphinids are top ocean predators and accumulate high concentrations of mercury (Hg) through the food chain, particularly in organs such as liver and kidney, although the proportion of methylmercury (MeHg) is relatively low due to the demethylation process. Total mercury (T-Hg) levels in marine mammals have been shown to correlate with selenium (Se) concentrations, and ingested MeHg that is demethylated may be present in tissues as mercury selenide (HgSe). In this study, we determined T-Hg, MeHg and Se concentrations of three Indo-Pacific bottlenose dolphins (Tursiops aduncus), and we used the individual with the highest Hg concentration for electron probe microanalysis to assess the co-localization of Hg and Se in the tissues. By electron probe microanalysis, we found that Hg and Se were co-localized in large granules in hepatic Kupffer cells and in small granules in hepatocytes. The analysis suggested that MeHg was demethylated in hepatocytes and then phagocytosed by Kupffer cells. In the kidney, Hg and Se were co-localized in the glomerular capillary wall and in interstitial blood vessel walls. Hg and Se were also co-localized in the cytoplasm of large neurons and in glial cells in the cerebrum. Divalent Hg and HgSe cannot cross the blood-brain barrier, suggesting that MeHg is demethylated in the dolphin brain and that binding to Se suppresses Hg toxicity.

Nitrospina-like Bacteria Are Dominant Potential Mercury Methylators in Both the Oyashio and Kuroshio Regions of the Western North Pacific.

Highly neurotoxic methylmercury (MeHg) accumulates in marine organisms, thereby negatively affecting human and environmental health. Recent studies have revealed that oceanic prokaryotes harboring the hgcAB gene pair are involved in Hg methylation. Presently, little is known about the distribution and phylogeny of these genes in distinct oceanic regions of the western North Pacific. In this study, we used metagenomics to survey the distribution of hgcAB genes in the seawater columns of the subarctic Oyashio region and the subtropical Kuroshio region. The hgcAB genes were detected in the MeHg-rich offshore mesopelagic layers of both the Oyashio region, which is a highly productive area in the western North Pacific, and the Kuroshio region, which has low productivity. Comparative analysis revealed that hgcAB genes belonging to the Nitrospina-like lineage were dominant in the MeHg-rich mesopelagic layers of both regions. These results indicate that Nitrospina-like bacteria are the dominant Hg methylators in the mesopelagic layers throughout the western North Pacific. IMPORTANCE MeHg is highly neurotoxic and accumulates in marine organisms. Thus, understanding MeHg production in seawater is critical for environmental and human health. Recent studies have shown that microorganisms harboring mercury-methylating genes (hgcA and hgcB) are involved in MeHg production in several marine environments. Knowing the distribution and phylogeny of hgcAB genes in seawater columns can facilitate assessment of microbial MeHg production in the ocean. We report that hgcAB genes affiliated with the microaerophilic Nitrospina lineage were detected in the MeHg-rich mesopelagic layers of two hydrologically distinct oceanic regions of the western North Pacific. This finding facilitates understanding of the microbial Hg methylation and accumulation in seawater columns of the western North Pacific.

Application of the Quartz Crystal Microbalance Method for Measuring Mercury in the Air of Working Environments Involved to Artisanal and Small-scale Gold Mining (ASGM).

Artisanal small gold mining (ASGM) is responsible for approximately 40% of the total Hg emissions into the atmosphere worldwide. In developing countries, many people are engaged in ASGM activities. We developed a small, simple Hg measuring device, which detects Hg in the air based on the change of the oscillation frequency of an Au electrode on a quartz crystal microbalance (QCM). This device is called QCM-Hg. We tested the viability of the QCM-Hg in various work settings including a gold mining area and gold shops. In working environments with an airborne Hg concentration of several µg m-3, the changing rate of the oscillation frequency for either 2 or 3 min corresponded with the Hg concentrations measured using the conventional method of gold amalgamation and cold vapor atomic absorption spectrometer (CVAAS). The results revealed that the QCM-Hg is a useful device for real-time Hg monitoring in actual working environments related to ASGM activities and Hg treatment facilities.

Nitrospina-Like Bacteria Are Potential Mercury Methylators in the Mesopelagic Zone in the East China Sea.

In natural environments, the production of neurotoxic and bioaccumulative methylmercury (MeHg) is mediated by microorganisms carrying the genes hgcA and hgcB. However, the contribution of these microorganisms to mercury (Hg) methylation or MeHg accumulation in the ocean is poorly understood. Here we determined the total Hg (THg) and MeHg concentrations in seawater samples and conducted a metagenomic survey of the hgcAB genes and functional modules involved in metabolic pathways in the East China Sea (ECS). In the metagenomic analyses, we used paired-end reads and assembled contigs for hgcAB enumeration and phylogenetic analyses in the seawater column. To evaluate the relative abundance of hgcAB in the metagenomic data, we estimated the abundance of recA (single-copy gene of bacteria) as well and then compared them. Moreover, the profiles of prokaryotic community composition were analyzed by 16S rRNA gene (V4 region) deep-sequencing. In the mesopelagic layers, the hgcA sequences were detected, and there was a positive correlation between hgcA abundance relative to the recA and MeHg concentrations. Thus, the quantification of the hgcA sequences could provide valuable information to evaluate the potential environments of microbial MeHg accumulation in the seawater column. A phylogenetic analysis using the assembled contigs revealed that all of the hgcA sequences in the mesopelagic layers were affiliated with Nitrospina-like sequences. The 16S rRNA gene analysis revealed that Nitrospinae were abundant in the mesopelagic layers. Although the lineages of Deltaproteobacteria, Firmicutes, and Spirochaetes were detected in the seawater column, their hgcAB sequences were not detected in our metagenomes, despite the fact that they are closely related to previously identified Hg methylators. The metabolic pathway analysis revealed that the modules related to sulfur and methane metabolism were prominent in the mesopelagic layers. However, no hgcA sequences affiliated with sulfate-reducing bacteria (SRB) or methanogens were detected in these layers, suggesting that these bacteria could not be strongly involved in the Hg accumulation in the seawater column. Our results indicate that Nitrospina-like bacteria with hgcAB genes could play a critical role in microbial Hg accumulation in the oxygenated mesopelagic layers of the ECS.

Mercury speciation in preserved historical sludge: Potential risk from sludge contained within reclaimed land of Minamata Bay, Japan.

In the latter half of the 1950s, a large amount of methylmercury (MeHg) was discharged directly into Minamata Bay, Japan by a chemical factory, resulting in the contamination of the fish and shellfish. Ultimately, an outbreak of MeHg intoxication, called Minamata disease, occurred. From 1977 to 1988, the Kumamoto Prefectural Government dredged and transferred sediments exceeding 25 µg/g of total mercury (THg, dry basis) into a strictly segregated area of the bay near the wastewater outlet, then this area was landfilled. We conducted analyses of the mercury speciation in preserved Minamata Bay sludge samples (collected from inside of the bay prior to the termination of the remediation project; n=4) and recent Minamata Bay sediments (collected outside the dredging area of the bay; n=5) to evaluate the potential risk of the sludge/sediment leakage from the reclaimed land to the Minamata Bay. Median THg (dry basis) concentrations were 241 µg/g for the preserved sludge, 6.1 µg/g for the recent Minamata Bay sediments, and 0.18 µg/g for a single control sample; median MeHg concentrations (percentage of MeHg in THg) were 108 ng/g (0.031%), 3.7 ng/g (0.12%), and 0.71 ng/g (0.41%), respectively. In all the samples, the MeHg% decreased exponentially with increasing THg concentration. The extractability of THg from each sample into seawater was shown to be much lower than that of MeHg. The extracted MeHg was 0.86% for the preserved sludge, 4.57% for the recent Minamata Bay sediments, and 7.89% for the control. The predominant chemical form of mercury in the preserved sludge containing the highest THg concentration was found to be stable ß-mercury sulfide (HgS) based on transmission electron microscopy linked with energy-dispersive X-ray spectroscopy (TEM-EDX) and X-ray absorption fine structure (XAFS) analyses.

Mercury and Selenium Localization in the Cerebrum, Cerebellum, Liver, and Kidney of a Minamata Disease Case.

Minamata disease is a methylmercury poisoning caused by consumption of marine food contaminated by man-made methylmercury environmental pollution, and its most prominent feature is marked pathological changes in the central nervous system. Morphological alterations are less pronounced in the liver and the kidney, although their mercury levels are higher than those of the brain. In marine mammals, methylmercury is known to be easily converted to inorganic mercury and it combines with selenium forming mercury selenide, which may counteract the toxicity of mercury. However, little is known about the formation of mercury and selenium complex in human organs. In the present study, we examined the cerebrum, cerebellum, liver, and kidney of a Minamata disease case to study the mercury and selenium localization using electron probe microanalysis. Our results indicated the mercury and selenium localization in the specified tissue of the brain, liver, and kidney such as glial cells, Kupffer cells, and renal tubules.

Development of a differential-absorption lidar system for measurement of atmospheric atomic mercury by use of the third harmonic of an LDS-dye laser.

A differential-absorption lidar system that uses a long-life transmitter for monitoring of atomic-mercury concentrations in the atmosphere has been developed. The third harmonic of a tunable dye laser with LDS 765 dye pumped by the second harmonic of a Nd:YAG laser was used as the emitted beam from the transmitter. By use of this system, atmospheric concentrations of atomic mercury of less than 0.4 part in 10(12) were measured. The time trend of the measured concentration agreed with that obtained by a conventional gold amalgamation method combined with atomic absorption spectroscopy on the ground.

Dry deposition fluxes and deposition velocities of trace metals in the Tokyo metropolitan area measured with a water surface sampler.

Dry deposition fluxes and deposition velocities (=deposition flux/atmospheric concentration) for trace metals including Hg, Cd, Cu, Mn, Pb, and Zn in the Tokyo metropolitan area were measured using an improved water surface sampler. Mercury is deposited on the water surface in both gaseous (reactive gaseous mercury, RGM) and particulate (particulate mercury, Hg(p)) forms. The results based on 1 yr observations found that dry deposition plays a significant if not dominant role in trace metal deposition in this urban area, contributing fluxes ranging from 0.46 (Cd) to 3.0 (Zn) times those of concurrent wet deposition fluxes. The deposition velocities were found to be dependent on the deposition of coarse particles larger than approximately 5 microm in diameter on the basis of model calculations. Our analysis suggests that the 84.13% diameter is a more appropriate index for each deposited metal than the 50% diameter in the assumed undersize log-normal distribution, because larger particles are responsible for the flux. The deposition velocities for trace metals other than mercury increased exponentially with an increase in their 84.13% diameters. Using this regression equation, the deposition velocities for Hg(p) were estimated from its 84.13% diameter. The deposition fluxes for Hg(p) calculated from the estimated velocities tended to be close to the mercury fluxes measured with the water surface sampler during the study periods except during summer.