Evidence that Pacific tuna mercury levels are driven by marine methylmercury production and anthropogenic inputs.

Pacific Ocean tuna is among the most-consumed seafood products but contains relatively high levels of the neurotoxin methylmercury. Limited observations suggest tuna mercury levels vary in space and time, yet the drivers are not well understood. Here, we map mercury concentrations in skipjack tuna across the Pacific Ocean and build generalized additive models to quantify the anthropogenic, ecological, and biogeochemical drivers. Skipjack mercury levels display a fivefold spatial gradient, with maximum concentrations in the northwest near Asia, intermediate values in the east, and the lowest levels in the west, southwest, and central Pacific. Large spatial differences can be explained by the depth of the seawater methylmercury peak near low-oxygen zones, leading to enhanced tuna mercury concentrations in regions where oxygen depletion is shallow. Despite this natural biogeochemical control, the mercury hotspot in tuna caught near Asia is explained by elevated atmospheric mercury concentrations and/or mercury river inputs to the coastal shelf. While we cannot ignore the legacy mercury contribution from other regions to the Pacific Ocean (e.g., North America and Europe), our results suggest that recent anthropogenic mercury release, which is currently largest in Asia, contributes directly to present-day human mercury exposure.

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.

Complex Mixtures of Brominated/Chlorinated Diphenyl Ethers and Dibenzofurans in Soils from the Agbogbloshie e-Waste Site (Ghana): Occurrence, Formation, and Exposure Implications.

The distribution and toxic equivalents (TEQs) of brominated and chlorinated dibenzo- p-dioxins/dibenzofurans (PBDD/Fs and PCDD/Fs) in soils from Agbogbloshie e-waste site (Ghana) were investigated. The composition of brominated/chlorinated dibenzofurans (PXDFs) and diphenyl ethers (PBDEs, PCDEs, and PXDEs) was examined using two-dimensional gas chromatography-time-of-flight mass spectrometry to elucidate possible formation pathways of dioxins from e-waste recycling. The highest concentrations of PCDD/Fs and PBDD/Fs were found, respectively, in the open burning (1.3-380 ng/g dry weight) and dismantling areas (11-1000 ng/g dry weight) and were comparable to the highest reported for informal e-waste sites. PXDFs and PXDEs were detected at up to the range of hundreds of nanograms per gram. The homologue profiles suggest that PXDFs were formed mainly from PBDFs through successive Br-to-Cl exchange. However, monobromo-PCDFs were also derived from de-novo-generated PCDFs in open burning areas. PBDFs contributed similar or higher TEQs (7.9-5400 pg/g dry weight) compared with PCDD/Fs (6.8-5200 pg/g dry weight), whereas PXDFs were also substantial TEQ contributors in open burning areas. The high TEQs of PBDFs in the dismantling area (120-5200 pg/g dry weight) indicate the need to consider brominated dioxins besides chlorinated dioxins in future studies on health implications for e-waste workers and local residents.

Mercury speciation and selenium in toothed-whale muscles.

Mercury accumulates at high levels in marine mammal tissues. However, its speciation is poorly understood. The main goal of this investigation was to establish the relationships among mercury species and selenium (Se) concentrations in toothed-whale muscles at different mercury levels. The concentrations of total mercury (T-Hg), methylmercury (MeHg), inorganic mercury (I-Hg) and Se were determined in the muscles of four toothed-whale species: bottlenose dolphins (n=31), Risso's dolphins (n=30), striped dolphins (n=29), and short-finned pilot whales (n=30). In each species, the MeHg concentration increased with increasing T-Hg concentration, tending to reach a plateau. In contrast, the proportion of MeHg in T-Hg decreased from 90-100% to 20-40%. The levels of T-Hg and Se showed strong positive correlations. Se/I-Hg molar ratios rapidly decreased with the increase of I-Hg and reached almost 1 in all species. These results suggested that the demethylated MeHg immediately formed Se/I-Hg equimolar complex of mercury selenide (HgSe) in their muscles. In addition, an X-ray absorption fine structure analysis (XAFS) of a bottlenose dolphin muscle confirmed that the dominant chemical form of the Se/I-Hg equimolar complex was HgSe. HgSe was mainly localized in cells near the endomysium using electron probe microanalysis (EPMA). These results suggested that the demethylated MeHg finally deposits within muscle cells of bottlenose dolphin as an inert HgSe.

Occurrence of halogenated contaminants in inland and coastal fish from Ghana: levels, dietary exposure assessment and human health implications.

Fish consumption is known to have several health benefits for humans. However, the accumulation of toxic contaminants, such as PCBs, PBDEs and HBCDs in fish could pose health hazards. These contaminants were measured in tilapia fish species collected from Ghana. Mean levels were PCBs (62 ng/g lw), PBDEs (7.3 ng/g lw) and HBCDs (1.2 ng/g lw) and the predominance of CB-153, CB-138, CB-180, BDE-47 and α-HBCD is in concordance with scientific literature. The congener profiles of PBDEs and PCBs in the fish suggest that sources of Penta- and Deca-BDE technical mixtures as well as technical PCB mixture (Clophen A60) exist in Ghana, while textile operations and associated release of untreated wastewater are likely to be significant sources of HBCDs. Comparison of the results with some reported studies showed moderate contamination in Ghana although Ghana is a developing country in Africa. Concentrations of PCBs measured in all the specimens in this study were below the food safety guidelines issued by the Food and Drug Administration, USA and the European Commission. The calculated hazard index levels of the target contaminants were below the threshold value of one, indicating that the levels of the target contaminants do not seem to constitute a health risk via fish consumption, with regard to PCBs, PBDEs and HBCDs, based on the limited number of samples that was accounted for in this study. However, due to the continuous discharge of untreated effluents, follow up studies are warranted as the consumption of fish is the primary route of human exposure to PCBs. This maiden report on the status of PBDEs and HBCDs in fish from Ghana will contribute to the knowledge about environmental contamination by POPs in a less industrialized region of the world so far sparsely covered in the literature.

Tissue-variation of iron stable isotopes in marine fish coupled with speciation analysis using X-ray absorption fine structure.

The Fe stable isotope ratio (δ56Fe) in tissues is a potential parameter for examining the Fe metabolism in marine fish. Although the effect of ferritin storage has been proposed as a possible cause of heavy isotope (56Fe) enrichment in the liver, no speciation and stable isotope ratio coupling data are available. Here, we report the δ56Fe values measured by multicollector ICP-MS and the result of Fe K-edge X-ray absorption near-edge structure (XANES) analysis of multiple tissues obtained from a skipjack tuna (Katsuwonus pelamis) and a chub mackerel (Scomber japonicus). Apparent isotopic fractionation between the liver and the muscle samples (Δ56FeL-M = Î´56Feliver - Î´56Femuscle) from these species was observed (0.85 ‰ and 0.57 ‰, respectively). The dominant Fe species in the muscle was heme Fe (the sum of methemoglobin, oxyhemoglobin, and deoxyhemoglobin), while ferritin was not detected according to the linear combination fitting of the XANES spectra. In the liver, ferritin contribution was ca. 28 %-54 % of the total Fe content. The apparent difference in δ56Fe between heme Fe and ferritin was estimated to range from 1.41 ‰ to 1.52 ‰ based on the tissue-specific δ56Fe values and the XANES results. These results indicate that the Fe storage as ferritin does not induce the lowering of δ56Fe in the muscle, considering the low contribution of the liver Fe to the total Fe content in the body.

Quantification of toxic metals derived from macroplastic litter on Ookushi Beach, Japan.

The potential risk of toxic metals that could leach into a beach environment from plastic litter washed ashore on Ookushi Beach, Goto Islands, Japan was estimated by balloon aerial photography, in situ beach surveys, and leaching experiments in conjunction with a Fickian diffusion model analysis. Chromium (Cr), cadmium (Cd), tin (Sn), antimony (Sb), and lead (Pb) were detected in plastic litter collected during the beach surveys. Polyvinyl chloride (PVC) fishing floats contained the highest quantity of Pb. Balloon aerial photography in conjunction with a beach survey gave an estimated mass of Pb derived from plastic litter of 313 ± 247 g. Lead leaching experiments on collected PVC floats showed that Pb in the plastic litter could leach into surrounding water on the actual beach, and that plastic litter may act as a "transport vector" of toxic metals to the beach environment. Using the experimental data, the total mass of Pb that could leach from PVC plastic litter over a year onto Ookushi Beach was estimated as 0.6 ± 0.6 g/year, suggesting that toxic metals derived from plastic beach litter are a potential "pathway" to contamination of the beach environment due to their accumulation in beach soil over time.

Hypoxia-induced exposure of isaza fish to manganese and arsenic at the bottom of Lake Biwa, Japan: experimental and geochemical verification.

In December 2007, a mass mortality of isaza (Gymnogobius isaza), a goby fish in Lake Biwa, Japan, was observed under severe hypoxia. Considering the level of manganese and arsenic in the dead isaza during the event was much higher than that in live isaza, hypoxia-induced mobilization of manganese and arsenic and subsequent exposure could be the reason for this adverse effect. However, secondary accumulation of manganese and arsenic after the mortality event could not be ruled out. To test this hypothesis, we conducted tissue distribution/speciation analysis and absorption tests on dead specimens. All the results, particularly the limited absorption of arsenic in the absorption tests, indicated that the isaza were exposed to arsenic before the mortality event. Parallel to this, the geochemical behavior of manganese and arsenic in oxygen-rich conditions (June) and oxygen-poor conditions (December) was investigated to verify the mechanism of exposure. Considerable enrichment of manganese and arsenic in a thin surface layer of sediment was a common feature in all seven stations studied. In the water at the bottom of the lake, a clear increase of arsenite in December was observed, and the manganese level was several hundred times higher in both seasons than the average level of the lake. Although further verification is needed, the data provided here support exposure to manganese and arsenic under hypoxia.

Broadband high-energy resolution hard x-ray spectroscopy using transition edge sensors at SPring-8.

We have succeeded in operating a transition-edge sensor (TES) spectrometer and evaluating its performance at the SPring-8 synchrotron x-ray light source. The TES spectrometer consists of a 240 pixel National Institute of Standards and Technology (NIST) TES system, and 220 pixels are operated simultaneously with an energy resolution of 4 eV at 6 keV at a rate of ∼1 c/s pixel-1. The tolerance for high count rates is evaluated in terms of energy resolution and live time fraction, leading to an empirical compromise of ∼2 × 103 c/s (all pixels) with an energy resolution of 5 eV at 6 keV. By utilizing the TES's wideband spectroscopic capability, simultaneous multi-element analysis is demonstrated for a standard sample. We conducted x-ray absorption near-edge structure (XANES) analysis in fluorescence mode using the TES spectrometer. The excellent energy resolution of the TES enabled us to detect weak fluorescence lines from dilute samples and trace elements that have previously been difficult to resolve due to the nearly overlapping emission lines of other dominant elements. The neighboring lines of As Kα and Pb Lα2 of the standard sample were clearly resolved, and the XANES of Pb Lα2 was obtained. Moreover, the x-ray spectrum from the small amount of Fe in aerosols was distinguished from the spectrum of a blank target, which helps us to understand the targets and the environment. These results are the first important step for the application of high resolution TES-based spectroscopy at hard x-ray synchrotron facilities.

Characterization of two types of cesium-bearing microparticles emitted from the Fukushima accident via multiple synchrotron radiation analyses.

A part of radiocesium emitted during the Fukushima nuclear accident was incorporated in glassy water-resistant microparticles, called Type-A particles, which are spherical with ~ 0.1 to 10 µm diameter and ~ 10-2 to 102 Bq cesium-137 (137Cs) radioactivity; they were emitted from Unit 2 or 3 of the Fukushima Daiichi Nuclear Power Plant. Meanwhile, Type-B particles, having various shapes, 50-400 µm diameter, and 101-104 Bq 137Cs radioactivity, were emitted from Unit 1. The chemical properties of these radioactive particles have been reported in detail, but previous studies investigated only a small number of particles, especially Type-B particles. We tried to understand radioactive particles systematically by analyzing a large number of particles. Micro-X-ray computed tomography combined with X-ray fluorescence analysis revealed the presence of many voids and iron-rich part within Type-B particles. The 137Cs concentration (Bq mm-3) of Type-A particles was ~ 10,000 times higher than that of Type-B particles. Among the Type-B particles, the spherical ones had higher concentration of volatile elements than the non-spherical ones. These differences suggested that Type-A particles were formed through gas condensation, whereas Type-B particles were formed through melt solidification. These findings might contribute to the safe decommissioning of reactors and environmental impact assessment.

Effects of Prenatal Methylmercury Exposure: From Minamata Disease to Environmental Health Studies.

Methylmercury, the causative agent of Minamata disease, can easily penetrate the brain, and adult-type Minamata disease patients showed neurological symptoms according to the brain regions where the neurons, mainly in the cerebrum and cerebellum, were damaged. In addition, fetuses are exposed to methylmercury via the placenta from maternal fish consumption, and high-level exposure to methylmercury causes damage to the brains of infants. Typical patients with fetal-type Minamata disease (i.e., serious poisoning caused by in utero exposure to methylmercury) were born during the period of severe methylmercury pollution in 1955-1959, although they showed no abnormality during gestation nor at delivery. However, they showed difficulties in head control, sitting, and walking, and showed disturbances in mental development, these symptoms that are similar to those of cerebral palsy, during the growth periods after birth. The impaired development of fetal-type Minamata disease patients was one of the most tragic and characteristic feature of Minamata disease. In this review, we first summarize 1) the effects of prenatal methylmercury exposure in Minamata disease. Then, we introduce the studies that were conducted mainly by Sakamoto et al. as follows: 2) a retrospective study on temporal and regional variations of methylmercury pollution in Minamata area using preserved umbilical cord methylmercury, 3) decline in male sex ratio observed in Minamata area, 4) characteristics of hand tremor and postural sway in fetal-type Minamata disease patients, 5) methylmercury transfer from mothers to infants during gestation and lactation (the role of placenta), 6) extrapolation studies using rat models on the effects of prenatal methylmercury exposure on the human brain, and 7) risks and benefits of fish consumption.

Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils.

We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS.

Release of chlorinated, brominated and mixed halogenated dioxin-related compounds to soils from open burning of e-waste in Agbogbloshie (Accra, Ghana).

Although complex mixtures of dioxin-related compounds (DRCs) can be released from informal e-waste recycling, DRC contamination in African e-waste recycling sites has not been investigated. This study examined the concentrations of DRCs including chlorinated, brominated, mixed halogenated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs, PBDD/Fs, PXDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in surface soil samples from the Agbogbloshie e-waste recycling site in Ghana. PCDD/F and PBDD/F concentrations in open burning areas (18-520 and 83-3800 ng/g dry, respectively) were among the highest reported in soils from informal e-waste sites. The concentrations of PCDFs and PBDFs were higher than those of the respective dibenzo-p-dioxins, suggesting combustion and PBDE-containing plastics as principal sources. PXDFs were found as more abundant than PCDFs, and higher brominated analogues occurred at higher concentrations. The median total WHO toxic equivalent (TEQ) concentration in open burning soils was 7 times higher than the U.S. action level (1000 pg/g), with TEQ contributors in the order of PBDFs>>PCDD/Fs>PXDFs. DRC emission to soils over the e-waste site as of 2010 was estimated, from surface soil lightness based on the correlations between concentrations and lightness, at 200mg (95% confidence interval 93-540 mg) WHO-TEQ over three years. People living in Agbogbloshie are potentially exposed to high levels of not only chlorinated but also brominated DRCs, and human health implications need to be assessed in future studies.

The potential of oceanic transport and onshore leaching of additive-derived lead by marine macro-plastic debris.

The long-distance transport potential of toxic lead (Pb) by plastic marine debris was examined by pure water leaching experiments using plastic fishery floats containing high level of additive-Pb such as 5100±74.3mgkg(-1). The leaching of Pb ended after sequential 480-h leaching experiments, and the total leaching amount is equivalent to approximately 0.1% of total Pb in a float. But it recovered when the float was scratched using sandpaper. We propose that a "low-Pb layer," in which Pb concentration is negligibly small, be generated on the float surface by the initial leaching process. Thickness of the layer is estimated at 2.5±1.2µm, much shallower than flaws on floats scratched by sandpaper and floats littering beaches. The result suggests that the low-Pb layer is broken by physical abrasion when floats are washed ashore, and that Pb inside the floats can thereafter leach into beaches.

Interplay of metals and bromine with dioxin-related compounds concentrated in e-waste open burning soil from Agbogbloshie in Accra, Ghana.

Open burning of electronic waste (e-waste) releases various metals and organohalogen compounds in the environment. Here we investigated the interplay of metals (Cu, Pb, Zn, Fe, Co, and Sr) and bromine (Br) in the formation of dioxin-related compounds (DRCs), including polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs), as well as non-regulated DRCs such as polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) and their monobrominated PCDD/Fs in soils sampled from open burning e-waste sites at Agbogbloshie in Accra, Ghana. The predominant DRCs were PBDFs, PCDFs, PCDDs, and DL-PCBs. Statistical analyzes, X-ray absorption spectroscopy, and the PCDF/PCDD ratio suggested possible formation paths of PCDD/Fs and DL-PCBs by catalytic behaviors of copper chlorides (CuCl, CuCl2, and Cu2(OH)3Cl) and thermal breakdown of polyvinyl chloride. Predominant formation of brominated furans may be derived from electron transfer from intermediates of PBDE to copper, Cu(II) â†’ Cu(I). Lead chloride also contributed to generate DRCs and may become highly bioaccessible through the open burning of e-waste. The main zinc species (ZnCl2 and ZnS) suggested a possible relationship to generate DRCs and specific zinc source such as tire burning. Cu, Pb, Zn, and Br contained in various e-wastes, wires/cables, plastics, and tires strongly influenced generation of many DRCs.

Lead in duplicate diet samples from an academic community.

Lead is a naturally occurring element that with the advent of the industrial era became a serious environmental and public health issue. Leaded gasoline, lead based paints, use of lead in plumbing and water pipes, ceramics with lead-containing glazes and tobacco smoke are potential sources of lead exposure for humans. Despite these multiple sources, food is still considered the most important one for the general non-smoking population. Hence, in the present study, the dietary intake of lead was determined in duplicate diet samples provided by 30 participants working or studying at University of Aveiro, Portugal. Pb was detected in all the analysed samples with values ranging between 0.009 and 0.10mgkg-1 ww which correspond to estimated daily intakes between 0.22 and 3.5µgkg-bw-1day-1. Risk estimations disclose that at least 3.3% and 26.7% of the participants might suffer cardiovascular and nephrotoxic effects, respectively.

Identification of anaerobic arsenite-oxidizing and arsenate-reducing bacteria associated with an alkaline saline lake in Khovsgol, Mongolia.

Microbial arsenic transformation pathways associated with a saline lake located in northern Mongolia were examined using molecular biological and culturing approaches. Bacterial 16S rRNA gene sequences recovered from saline lake sediments and soils were affiliated with haloalkaliphiles, including Bacillus and Halomonas spp. Diverse sequences of arsenate respiratory reductase (arrA) and a new group of arsenite oxidase (arxA) genes were also identified. Pure cultures of arsenate-reducing Nitrincola strain and anaerobic arsenite-oxidizing Halomonas strain were isolated. The chemoorganotrophic Halomonas strain contains arxA gene similar to that of a chemoautotrophic arsenite-oxidizing Alkalilimnicola ehrlichii strain MLHE-1. These results revealed the diversity of arsenic transformation pathways associated with a geographically distinct saline system and the potential contribution of arx-dependent arsenite oxidation by heterotrophic bacteria.

Variation and distribution of metals and metalloids in soil/ash mixtures from Agbogbloshie e-waste recycling site in Accra, Ghana.

Illegal import and improper recycling of electronic waste (e-waste) are an environmental issue in developing countries around the world. African countries are no exception to this problem and the Agbogbloshie market in Accra, Ghana is a well-known e-waste recycling site. We have studied the levels of metal(loid)s in the mixtures of residual ash, formed by the burning of e-waste, and the cover soil, obtained using a portable X-ray fluorescence spectrometer (P-XRF) coupled with determination of the 1M HCl-extractable fraction by an inductively coupled plasma mass spectrometer. The accuracy and precision of the P-XRF measurements were evaluated by measuring 18 standard reference materials; this indicated the acceptable but limited quality of this method as a screening tool. The HCl-extractable levels of Al, Co, Cu, Zn, Cd, In, Sb, Ba, and Pb in 10 soil/ash mixtures varied by more than one order of magnitude. The levels of these metal(loid)s were found to be correlated with the color (i.e., soil/ash ratio), suggesting that they are being released from disposed e-waste via open burning. The source of rare elements could be constrained using correlation to the predominant metals. Human hazard quotient values based on ingestion of soil/ash mixtures exceeded unity for Pb, As, Sb, and Cu in a high-exposure scenario. This study showed that along with common metals, rare metal(loid)s are also enriched in the e-waste burning site. We suggest that risk assessment considering exposure to multiple metal(loid)s should be addressed in studies of e-waste recycling sites.

Concentrations of trace elements in American alligators (Alligator mississippiensis) from Florida, USA.

Concentrations of 28 trace elements (Li, Mg, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Tl, Hg, Pb, and Bi) in the livers of juvenile and adult American alligators inhabiting two central Florida lakes, Lake Apopka (LA), and Lake Woodruff National Wildlife Refuge (LW) and one lagoon population located in Merritt Island National Wildlife Refuge (MINWR; NASA), were determined. In juveniles from MINWR, concentrations of nine elements (Li, Fe, Ni, Sr, In, Sb, Hg, Pb and Bi) were significantly higher, whereas six elements (V, Fe, As, Sr, Hg and Bi) were elevated in adults (p<0.05) obtained from MINWR. Significant enrichment of some trace elements in adults, relative to juveniles, was observed at all three sampling areas. Specifically, Fe, Pb and Hg were significantly elevated in adults when compared to juveniles, suggesting age-dependent accumulation of these elements. Further, As, Se and Sn showed the same trend but only in animals collected from MINWR. Mean Fe concentrations in the livers of adults from LA, LW and MINWR were 1770 µg g(-1) DW, 3690 µg g(-1) DW and 5250 µg g(-1) DW, respectively. More than half of the adult specimens from LW and MINWR exhibited elevated hepatic Fe concentrations that exceed the threshold value for toxic effects in donkey, red deer and human. These results prompted us to express our concern on possible exposure and health effects in American alligators by some trace elements derived from NASA activities.

Identification of antimony- and arsenic-oxidizing bacteria associated with antimony mine tailing.

Antimony (Sb) is a naturally occurring toxic element commonly associated with arsenic (As) in the environment and both elements have similar chemistry and toxicity. Increasing numbers of studies have focused on microbial As transformations, while microbial Sb interactions are still not well understood. To gain insight into microbial roles in the geochemical cycling of Sb and As, soils from Sb mine tailing were examined for the presence of Sb- and As-oxidizing bacteria. After aerobic enrichment culturing with As(III) (10 mM) or Sb(III) (100 µM), pure cultures of Pseudomonas- and Stenotrophomonas-related isolates with Sb(III) oxidation activities and a Sinorhizobium-related isolate capable of As(III) oxidation were obtained. The As(III)-oxidizing Sinorhizobium isolate possessed the aerobic arsenite oxidase gene (aioA), the expression of which was induced in the presence of As(III) or Sb(III). However, no Sb(III) oxidation activity was detected from the Sinorhizobium-related isolate, suggesting the involvement of different mechanisms for Sb and As oxidation. These results demonstrate that indigenous microorganisms associated with Sb mine soils are capable of Sb and As oxidation, and potentially contribute to the speciation and mobility of Sb and As in situ.