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1.
Terrestrial snails are consumed by humans occasionally and they are an important food source for many creatures including fish and birds. Little is known about arsenic speciation in these gastropods, let alone life cycle variations. Here we report on the arsenic speciation in freshwater snails from Pender Island and Vancouver Island, B.C., Canada, which was determined on methanol/water extracts (43-59% extraction efficiency) by using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and HPLC-electrospray tandem mass spectrometry. The tetramethylarsonium ion, oxo-arsenosugars and thio-arsenosugars are the main arsenic species encountered. Arsenobetaine, which is commonly found in the marine environment, is minor. Live bearing snails Viviparidae sp. from Pender Island were maintained in aquaria and the arsenic speciation in the unborn, newly born, and adult animals was monitored. Oxo-arsenosugars predominate in the adults, whereas thio-arsenosugars seem to predominate in juveniles, suggesting that these arsenicals are snail metabolites.  相似文献   

2.
Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.  相似文献   

3.
The relationship between the total arsenic concentration and the chemical speciation of arsenic in two species of earthworm (Lumbricus rubellus and Dendrodrilus rubidus) in relation to the host soil, was investigated for 13 sites of varying arsenic content, including a background level garden soil and a former mine site at the Devon Great Consols, UK. Earthworms were collected with the host soil (As soil concentration range 16-12, 466 mg kg(-1) dry weight) and measured for their total arsenic (concentration range 7-595 mg kg(-1) dry weight) using inductively coupled plasma mass spectrometry (ICP-MS). A methanol-water mixture was used to extract arsenic species from the earthworms prior to determination of the individual arsenic species by a combination of anion and cation exchange high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A gradient elution anion exchange method is presented whereby nine arsenic species could be measured in one sample injection. Arsenic species were identified by comparison of retention times and sample spiking with known standards and a fully characterised seaweed extract. Arsenic was generally present in the earthworm as arsenate (As(V)) or arsenite (As(III)) and arsenobetaine (AB). Methylarsonate (MA), dimethylarsinate (DMA) and three arsenosugars (glycerol, phosphate, sulfate) were present as minor constituents. These results are discussed in relation to the mechanisms for coping with exposure to soil bound arsenic.  相似文献   

4.
Arsenic speciation in natural surface-water systems can be highly impacted through biological processes that result in non-thermodynamically predicted species to dominate the system. In laboratory experiments, arsenate reduction by a freshwater cyanobacterium exhibited saturation kinetics increasingly inhibited by elevating solution phosphate concentrations. Approximately 100% arsenate reduction occurred by days 4, 7, and 10 in the low (0.35 μm), middle (3.5 μm), and high (35 μm) phosphate treatments, respectively, with maximum arsenate reduction rates ranged from 0.013 μmol As g C−1 day−1 in the high-phosphate treatment to 0.398 μmol As g C−1 day−1 in the low-phosphate treatment. Saturation kinetic models were utilized to evaluate the impact of cell growth and arsenate-phosphate uptake competition on arsenate reduction rates by the cyanobacterium. Results showed reduced arsenicals dominate arsenic speciation once growth reached steady state, indicating reduced arsenicals may dominate natural systems, even when considering conservatively high, abiotic arsenic reoxidation.  相似文献   

5.
Interests in the determination of different arsenic species in natural waters is caused by the fact that toxic effects of arsenic are connected with its chemical forms and oxidation states. In determinations of water samples inorganic arsenate (As(III), As(V)), methylated metabolities (MMAA, DMAA) and other organic forms such as AsB, AsC, arsenosugars or arsenic containing lipids have the most importance. This article provides information about occurrence of the dominant arsenic forms in various water environments. The main factors controlling arsenic speciation in water are described. The quantification of species is difficult because the concentrations of different forms in water samples are relatively lowcompared to the detection limits of the available analytical techniques. Several hyphenated methods used in arsenic speciation analysis are described. Specific advantages and disadvantages of methods can define their application for a particular sample analysis. Insufficient selectivity and sensitivity of arsenic speciation methods cause searching for a new or modifications already existing techniques. Some aspects of improvement and modifications of the methods are highlighted.  相似文献   

6.
In 1991 and 1992 we determined the levels of metals, arsenic, boron, and selenium in the Neosho River drainage in southeastern Kansas, the primary habitat for the threatened Neosho madtom (Noturus placidus). We evaluated concentrations in sediments, mussels (Quadrula pustulosa and Q. metanevra), and fish(Percina phoxocephala, Cyprinus carpio,and Ictiobus bubalus) from three sites on theNeosho River and one site on the Cottonwood River. We also evaluated contaminant concentrations in C. carpio composite samples collected by theKansas Department of Health and Environment (KDHE)at two additional locations on the Neosho River in1990–92. Sediments were contaminated by lead. Concentrations of selenium, boron, and most metalsin mussels were low to normal for biota. Arseniclevels in mussels and fish suggest low-levelcontamination of biota. Aluminum, barium, manganeseand strontium concentrations were much higher inmussels than in fish. Five fish composite sampleshad cadmium concentrations that indicate chronicdeleterious effects on biota. Lead concentrationsin six fish samples were elevated. Mercuryconcentrations in most large fish compositesexceeded concentration for protection of animalsthat might consume them. We believe that reductionsin cadmium, lead, and mercury contamination, inparticular, would benefit aquatic life in theriver.  相似文献   

7.
The National Biomonitoring Specimen Bank (NBSB), established in 1979 at the NIST Neutron Research Facility, Gaithersburg, Maryland, was specifically designed to store environmental specimens over long periods of time (50-100 years). This bank contains specimens (e.g., human livers, marine sediments, fish tissues, mussels, oysters, human diet samples, and marine mammal tissues) collected as part of several monitoring and research programs supported by U.S. Federal agencies. In 2002, NIST completed the construction of a second environmental specimen bank facility specifically designed for supporting monitoring and research on marine environmental health issues. This facility, the Marine Environmental Specimen Bank (Marine ESB) is located at the Hollings Marine Laboratory in Charleston, South Carolina, in partnership with a U.S. Federal resource agency, two universities, and a State of South Carolina resource agency. The Marine ESB provides a resource of research specimens that are used to address questions regarding temporal and geographic trends in environmental contamination, genetic separation of populations of animals, and the health status of various types of marine animals. Specimens banked include marine mammal tissues, bird tissues, mussels, and oysters. Plans are underway to establish protocols and initiate banking procedures for other types of marine organisms and environmental materials as part of an expanded effort to support research on the health of marine biota.  相似文献   

8.
In the year 2000, organotin pollution was investigated in the Bay of Piran, Slovenia, at the northern extremity of the Adriatic Sea. Gas chromatography-mass spectrometry with single ion monitoring GC/MS-SIM was applied for speciation analysis of pentylated organotin compounds in water and mussels. Sampling of marine waters was performed in summer and autumn at 8 locations. Mussels Mytilus galloprovincialis were collected only in summer at 3 locations. The highest concentrations of tributyltin (TBT) in marine water ranged from 500 to 630 ng L(-1) (as Sn) in summer and from 180 to 230 ng L(-1) (as Sn) in autumn. TBT concentration in mussels varied from 500 to 3500 ng g(-1) dry weight (d.w.) (as Sn). The study indicated remarkable butyltin pollution of the Slovenian coastline. Accuracy of the analytical procedure was verified by BCR CRM 477.  相似文献   

9.
Although octachlorostyrene (OCS) was never used as a commercial product, it may be produced during incineration and combustion processes involving chlorinated compounds. Its environmental spreading was evaluated through the analysis of several representative samples. OCS could not be measured in soil samples collected from urban and rural areas or sediments, but was present (up to 5.41 ng/g dry weight) in industrial soil collected near chemically polluted areas. For aquatic biota samples, the OCS concentrations in freshwater mussels ranged from <0.01 ng/g wet weight (ww) to 0.18 ng/g ww (mean 0.06 ng/g ww) and similar levels could be measured in 11 freshwater fish species from Belgium and Romania. A higher OCS contamination level was found in shrimps (mean 0.08 ng/g ww) compared to marine fish (mean 0.02 ng/g ww for bib and 0.01 ng/g ww for sole and whiting, respectively). OCS could also be measured in 19 harbour porpoise (Phocoena phocoena) liver samples with a mean value of 1.90 ng/g ww. According to these data, it could be computed that the biomagnification factor for OCS was one order of magnitude lower than that of HCB in the fish-porpoise food chain. The mean OCS concentrations in blue tits (Parus caeruleus) eggs and great tits (Parus major) adipose tissue were 1.24 ng/g ww and 3.24 ng/g ww, respectively. OCS could be measured in different tissues of hedgehog (Erinaceus europaeus), with the highest concentrations found in adipose tissue (mean 0.34 ng/g ww) and liver (mean 0.39 ng/g ww). In contrast, only low concentrations of OCS could be measured in human adipose tissue (up to 0.38 ng/g ww) and liver (up to 0.05 ng/g ww), while it could not be detected in human brain or lung. The relationship between the concentrations of OCS and HCB was also discussed for each species.  相似文献   

10.
The polycyclic musk compounds HHCB (Galaxolide) and AHTN (Tonalide) are commonly used as synthetic fragrances in personal care products and household cleaners. These and other synthetic musk fragrances were quantified in different aquatic samples from the German Environmental Specimen Bank (ESB). While HHCB and AHTN were found in almost all samples, most of the other musk fragrances were detected only in a few samples and mostly at lower concentration levels. Blue mussels from the North Sea showed varying levels of 0.5-1.7 ng g(-1) ww for HHCB and 0.4-2.5 ng g(-1) ww for AHTN (ww, wet weight) in the period from 1986 to 2000, while blue mussels from the Baltic Sea were only slightly contaminated with synthetic musk fragrances. Lipid weight-related concentrations of synthetic musk compounds in blue mussels were higher than in eelpout muscles, bladder wrack and herring gull eggs. In comparison to the marine specimens, muscles of bream from German rivers had higher concentrations of HHCB and AHTN. The ranges of HHCB and AHTN concentrations in bream from the Elbe River were 545-6400 ng g(-1) lw and 48-2130 ng g(-1) lw, respectively (lw, lipid weight; five sampling sites, period 1993-2003). In the Rhine River, HHCB and AHTN levels of bream muscles were highest at the Iffezheim site (up to 9750 ng g(-1) lw HHCB, 1998). Even higher synthetic musk levels were detected in bream from the rivers Saale and Saar. In recent years, levels of both compounds determined in bream from most sampling sites have decreased from maximum values in the 1990s. As the concentrations of AHTN have decreased faster, the ratio of HHCB to AHTN increased from 2-4 in the 1990s to 10-20 in recent years.  相似文献   

11.
For decades there has been an intense interest in the toxic effects of trace metals on biological organisms in the environment. This period of time has seen increasing improvements in analytical techniques for the measurement and study of trace metals and their subsequent application to a broad spectrum of water systems around the globe. This work has included studies of the geographical distributions of trace metals in different water types in the ocean, the modes of transport and uptake of trace metals and the study of historical changes in trace metal accumulation. Early research highlighted strong similarities in the behaviours of many trace metals and those of well-understood chemical nutrients such as phosphate, nitrate and silicate, known to be essential for phytoplankton growth in the ocean. This suggests that phytoplankton regulate the trace metal composition of seawater for their own benefit. A major achievement in this regard has been the ability to measure, at the sub-nmol/L level, trace metal species that are complexed by naturally-occurring organic ligands of biological origin in ocean waters. It is now clear that the free ion activities of many essential and/or toxic trace metals are regulated by highly specific, strongly complexing ligands exuded by marine phytoplankton. This research encourages a new paradigm in which the growth rates and species composition of primary marine organisms are affected by trace metals at concentration levels orders of magnitude lower than is conventionally believed. As a consequence, the capacity of natural waters to assimilate trace metal-contaminants may be correspondingly much lower than is currently thought reasonable.  相似文献   

12.
Arsenic speciation was determined in Lumbricus rubellus Hoffmeister from arsenic-contaminated mine spoil sites and an uncontaminated site using HPLC-MS, HPLC-ICP-MS and XAS. It was previously demonstrated that L. rubellus from mine soils were more arsenate resistant than from the uncontaminated site and we wished to investigate if arsenic speciation had a role in this resistance. Earthworms from contaminated sites had considerably higher arsenic body burdens (maximum 1,358 mg As kg-1) compared to the uncontaminated site (maximum 13 mg As kg-1). The only organo-arsenic species found in methanol/water extracts for all earthworm populations was arsenobetaine, quantified using both HPLC-MS and HPLC-ICP-MS. Arsenobetaine concentrations were high in L. rubellus from the uncontaminated site when concentrations were expressed as a percentage of the total arsenic burden (23% mean), but earthworms from the contaminated sites with relatively low arsenic burdens also had these high levels of arsenobetaine (17% mean). As arsenic body burden increased, the percentage of arsenobetaine present decreased in a dose dependent manner, although its absolute concentration rose with increasing arsenic burden. The origin of this arsenobetaine is discussed. XAS analysis of arsenic mine L. rubellus showed that arsenic was primarily present as As(III) co-ordinated with sulfur (30% approx.), with some As(v) with oxygen (5%). Spectra for As(III) complexed with glutathione gave a very good fit to the spectra obtained for the earthworms, suggesting a role for sulfur co-ordination in arsenic metabolism at higher earthworm arsenic burdens. It is also possible that the disintegration of As(III)-S complexes may have taken place due to (a) processing of the sample, (b) storage of the extract or (c) HPLC anion exchange. HPLC-ICP-MS analysis of methanol extracts showed the presence of arsenite and arsenate, suggesting that these sulfur complexes disintegrate on extraction. The role of arsenic speciation in the resistance of L. rubellus to arsenate is considered.  相似文献   

13.
The content of total arsenic, the inorganic forms: arsenite (As(III)) and arsenate (As(V)), the methylated forms: monomethylarsonic acid and dimethylarsinic acid (DMA), trimethylarsenic oxide, tetramethylarsenonium ion and arsenobetaine was measured in 95 sediment samples and 11 pore water samples from the Baltic Sea near the island of Bornholm at depths of up to 100 m. As(III+V) and DMA were detected in the sediment and As(III+V) was detected in the sediment pore water. Average total As concentration of 10.6?±?7.4 mg/kg dry matter (DM) in the sediment corresponds to previously reported values in the Baltic Sea and other parts of the world. Existing data for on-site measurements of sorption coefficients (Kd) of arsenicals in marine and freshwater sediments show large variability from <1 to >1,000 L/kg. In this work, calculated sorption coefficients (Kd and Koc) for As(III+V) showed significant correlation with depth, dissolved oxygen (DO), salinity and sediment classification; for depths <70 m, salinity <11 %, DO >9 mg/L and sand/silt/clay sediments the Kd was 118?±?76 L/kg DM and for depths >70 m, salinity >11 %, DO?<?9 mg/L and muddy sediments the Kd was 513?±?233 L/kg DM. The authors recommend using the found Kd value for arsenic in marine sediments when conditions are similar to the Baltic Sea. At locations with significant anthropogenic point sources or where the local geology contains volcanic rock and sulphide mineral deposits, there may be significantly elevated arsenic concentrations, and it is recommended to determine on-site Kd values.  相似文献   

14.
A recently developed method for the determination of arsenic species (arsenite, arsenate, monomethylarsonate, MMAA, and dimethylarsinate, DMAA) has been applied to the study of arsenic speciation in plants. This method uses ion-exchange liquid chromatography coupled on-line to atomic fluorescence spectrometry through continuous hydride generation. Various extraction procedures have been studied in detail using three plant certified reference materials. None of the procedures tested revealed fully satisfying results with all kinds of plant samples; microwave assisted extraction with 0.3 mol dm-3 orthophosphoric acid was found to be the most convenient for dealing with terrestrial plants. Species stability appears good. This method was applied to real world cultivated plant parts. Arsenate appears to predominate in soils, roots and leaves; unidentified species (probably arsenosugars) play an important role (60%) in rice fruits. Carrot was found to be the most contaminated edible plant part, containing 1 mg kg-1 essentially as arsenate species. MMAA was detected in all soils and some plant parts especially shallots at low levels, whereas DMAA was found only in one soil sample and in hot pepper leaves. Arsenite is a minor component of all soils; it is also present in some plant parts at low levels. However, no evident relationships were found between As speciation in the various plant parts and much more detailed studies will be necessary to elucidate As behaviour in plants.  相似文献   

15.
To examine the state of pollution of Bizerte Lagoon which is exposed to intense anthropogenic pressure, two sediment cores were taken at two sites, one undergoes the dual effects of both marine waters arriving from the Mediterranean Sea through the Channel, and also of freshwater from the Tinja River; the other core is located at the center of the lagoon where water depth is maximal (12 m). Heavy metal concentrations in the two cores were assessed, with calculated enrichment factors and geo-accumulation indexes. Core sediments were also studied for chemical speciation and their monosulfide contents were measured. Results from enrichment factors and geo-accumulation indexes show an accumulation of Cd, Zn, Cr, and Pb, while chemical speciation revealed a risk only from Cd and Mn. Comparison of sequential extraction values with those of acid volatile sulfides revealed that non-toxic effects may be caused by any of the studied metals in the sediment.  相似文献   

16.
Populations of invasive fishes quickly reach extremely high biomass. Before control methods can be applied, however, an understanding of the contaminant loads of these invaders carry is needed. We investigated differences in concentrations of selected elements in two invasive carp species as a function of sampling site, fish species, length and trophic differences using stable isotopes (delta (15)N, delta (13)C). Fish were collected from three different sites, the Illinois River near Havana, Illinois, and two sites in the Mississippi River, upstream and downstream of the Illinois River confluence. Five bighead carp (Hypophthalmichthys nobilis) and five silver carp (Hypophthalmichthys molitrix) from each site were collected for muscle tissue analyses. Freshwater mussels (Amblema plicata) previously collected in the same areas were used as an isotopic baseline to standardize fish results among sites. Total fish length, trophic position, and corrected (13)C, were significantly related to concentrations of metals in muscle. Fish length explained the most variation in metal concentrations, with most of that variation related to mercury levels. This result was not unexpected because larger fish are older, giving them a higher probability of exposure and accumulation of contaminants. There was a significant difference in stable isotope profiles between the two species. Bighead carp occupied a higher trophic position and had higher levels of corrected (13)C than silver carp. Additionally bighead carp had significantly lower concentrations of arsenic and selenium than silver carp. Stable isotope ratios of nitrogen in Asian carp were at levels that are more commonly associated with higher-level predators, or from organisms in areas containing high loads of wastewater effluent.  相似文献   

17.
An intertidal site in the Clyde Estuary, UK, was selected to evaluate the role of sediment geochemistry on the bioaccumulation of polychlorinated biphenyls (PCBs) by mussels (Mytilus edulis). The area had previously been identified as showing anomalously high levels of PCB contamination (over 1,500 microg kg(-1) total PCB in sediment, 22 congeners). Samples of surface sediment and M. edulis were collected from two closely located sites, one within the anomalous area and another representing typical PCB contamination in the estuary. Sediment samples were separated into grain size fractions and analysed for a range of biomarker compounds, PCBs and sediment mineralogy. The anomalous site showed an atypical association of PCBs with sediment properties, despite both locations showing influence of both petrogenic and pyrogenic organic contamination. Interrogation of data using correlation and principal component analysis showed that sediment mineralogy as well as organic matter composition influenced PCB congener distribution. One sediment source was found to control the PCB concentration in mussels at both locations and clay mineralogy appears to control PCB uptake by biota with preference for higher molecular weight congeners. Overall bioavailability is determined by sediment TOC.  相似文献   

18.
Estuaries are marine areas at great contamination risk due to their hydrodynamic features. PAH are wide and ubiquitous contaminants with a high presence in these marine environments. Chemical analysis of sediments can provide information, although it does not give a direct measure of the toxicological effect of such contaminants in the biota. Samples of Venerupis pullastra, Cerastoderma edule, and Mytilus galloprovincialis were collected from two locations in Corcubión estuary (Norhwest of Spain). The level of PAH in sediment and biota, and its possible origin were assessed. A moderate level of contamination was observed with a predominance of PAH of a pyrogenic origin. Genotoxic damage, measured as single-strand DNA breaks with the comet assay, was evaluated in gill tissue and in hemolymph. The values of DNA damage obtained showed a higher sensitivity of clams and cockles to the pollution load level. These differences among species make us suggest the use of some other species coupled with mussels as an optimal tool for biomonitoring estuarine environments.  相似文献   

19.
This paper presents preliminary data on polybrominated diphenyl ethers (PBDEs) in the Scottish aquatic environment. Sediment and biota (fish liver, fish muscle and mussels) from a number of locations around Scotland were analysed for PBDEs with samples being from both remote and from potentially contaminated areas such as the former sewage sludge dump site at Garroch Head in the Clyde. PBDEs were measured in both cultivated, rope grown mussels and wild mussels collected from 5 sites around Scotland in 2006. Total PBDE concentrations (sum of tri- to hepta-BDEs) ranged from 相似文献   

20.
Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.  相似文献   

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