Estimation of metal and organochlorine pesticide exposures and potential health threat by consumption of oysters in Taiwan

Pollutant concentrations detected in oysters from 12 different culture areas of Taiwan (especially for the Hsiangshan area and the Machu Islands) from 1991-98 were evaluated to investigate potential carcinogenic (inorganic As and organochlorine pesticides) and non-carcinogenic (Cu, Zn, Cd and inorganic As) risk to the public from ingestion of the oysters. The highest geometric mean (GM) Cu and Zn concentrations of 1108 (range 113-2806) and 1567 (range 303-3593) microg/g dry weight were obtained in oysters from the Hsiangshan coastal area. The maximum GM Cd and As concentrations of 6.82 and 19.3 microg/g dry weight were found in oysters from the Machu Islands area. The p,p'-DDE values range from not detectable in Penghu Islands' oysters to 164 ng/g dry weight in Machu Islands' oysters. The highest tDDT (sum of p,p'-DDE, p,p'-DDD and p,p'-DDT) concentrations of 337 and 340 ng/g dry weight were found in oysters from Kimmen and Machu Islands, respectively. A calculated target hazard quotient (THQ; daily intake/reference dose) of 11.4 (based on 139 g oysters/day) for Cu caused by consuming oysters from the Hsiangshan area is higher than that from other areas (range 0.124-5.95). The highest average Cu intake from Hsiangshan's oysters for individuals is 11.4 times (i.e. THQ=11.4) more than that of reference dose (40 microg/kg/day). However, the maximum THQ values for Cd and As caused by consuming oysters collected from the Machu Islands were 5.57 and 2.63 for Cd and As, respectively. Generally, the results of THQ showed that if only the maximally exposed individuals were considered, the value of 65.4% for oyster was higher than 1.0 in comparison with reference dose. All cancer risk estimates for inorganic As from consuming oysters were higher than 10(-6) (range from 128x10(-6) to 509x10(-6) for maximally exposed individuals and range from 17.1x10(-6) to 68.0x10(-6) for typically exposed individuals, respectively); that is the risk of the lower end of the range of acceptable risk. The highest risk estimate for inorganic As was 509x10(-6) for consumption of oysters by Machu Islands' residents. The lifetime cancer risks of 19.0x10(-6) for tDDT by consuming oysters from the Machu Islands was higher than those from the Penghu Islands (0.37x10(-6)). Therefore, the sum of lifetime cancer risks for tDDT and inorganic As had the highest risks (total risk=528x10(-6)) of consuming oysters from the Machu Islands. Furthermore, a 10(-6) upper limit on lifetime risk as the health protection standard would require maximum oyster consumption rates of approximately 0.26 g/day.     

Distribution of butyltin and derivatives in oyster shells and trapped sediments of two estuaries in Cantabria (Northern Spain)

Distribution of butyltin compounds (BTs) and derivatives (monobutyltin, MBT; dibutyltin, DBT and tributyltin, TBT) was analysed in Crassostrea gigas oyster shells and the sediments trapped in the shell chambers, from two different estuaries in Cantabria (Northern Spain), with very different environmental conditions, where previous data have not been reported. Inorganic tin analysis in oyster shells was performed in order to study the degradation of BTs. Shell thickening and losses in biological growth are related with the presence of TBT, and were determined using three morphological indexes. Total BTs concentrations, expressed as Sn, ranged from 18.0 ng g(-1) to 176.7 ng g(-1) in sediments, and from 2.4 ng g(-1) to 11.1 ng g(-1) in oyster shells. Total inorganic tin concentrations ranged from 1775.0 ng g(-1) to 4781.3 ng g(-1) in oyster shells. The amount of BTs in oyster shells has been associated with the concentrations in the sediments trapped in the shell chambers. Partition coefficients between oyster sediments and oyster shells show the affinity of BTs by the sediments and the higher inorganic tin in oyster shells does not seem to be related to the BTs pollution.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

Polybrominated diphenyl ethers in whitefish from Swiss lakes and farmed rainbow trout

A method for trace analysis of polybrominated diphenyl ethers (PBDE) in fish based on gas chromatography/electron ionization high resolution mass spectrometry (GC/EI-HRMS) was developed, and levels of PBDE were determined in whitefish (Coregonus sp.) from eight Swiss lakes and in rainbow trout (Oncorhynchus mykiss) from four Swiss fish farms. PBDE concentrations (sum of PBDE congeners BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) in filet from whitefish between 36 and 165 ng/g lipid weight (lw) were found, corresponding to wet weight (ww) concentrations of 1.6-7.4 ng/gww. PBDE contents in filet from farmed rainbow trout were significantly lower than in wild whitefish (12-24 ng/glw, 0.74-1.3 ng/gww), and the PBDE congener patterns were different for both species (a higher BDE-47 to BDE-99 ratio for farmed rainbow trout compared to wild whitefish was found). Whitefish PBDE levels [ng/glw] correlate better with the surface/volume ratio of the respective lakes (r(2)=0.70) than with other lake properties such as catchment area (size or number of inhabitants) or residence time, suggesting atmospheric deposition as an input pathway for PBDE. Based on an average daily consumption of 20 g whitefish (Switzerland) with a PBDE content of 7.4 ng/gww (highest PBDE concentration detected in this study), a maximum daily intake of 0.15 microg PBDE was estimated (0.026 microg/day for farmed trout). This number corresponds to the lower end of the estimate for the total PBDE intake of the Nordic consumer of 0.2-0.7 microg/day.     

Atomic absorption spectrometric determination of inorganic and organic arsenic in some marine benthic algae of the southern atlantic coasts

Arsenic in the inorganic and organic forms was analyzed in species of marine macro-algae growing in the South Atlantic Ocean. Species of the genera Lessonia, Gigartina, Adenocystis, Leathesia and Colpomenia were investigated. Arsenic accumulation was found in all species studied. Total As content ranged from 5.3 to 56.9 microg As g(-1) and the levels of the inorganic forms ranged from 0.2 to 2.0 microg As g(-1). The complete analytical procedure was validated against a standard reference material (NBS, SRM 1572, citrus leaves) and the value obtained was in good agreement with the certified value. Some commercial seaweed products were also analyzed.     

Polycyclic aromatic hydrocarbon (PAH) contamination of surface sediments and oysters from the inter-tidal areas of Dar es Salaam, Tanzania

Surface sediment and oyster samples from the inter-tidal areas of Dar es Salaam were analyzed for 23 polycyclic aromatic hydrocarbons (PAHs) including the 16 compounds prioritized by US-EPA using GC/MS. The total concentration of PAHs in the sediment ranged from 78 to 25,000 ng/g dry weight, while oyster concentrations ranged from 170 to 650 ng/g dry weight. Hazards due to sediment contamination were assessed using Equilibrium Partitioning Sediment Benchmarks and Threshold Effect Levels. Diagnostic indices and principle component analysis were used to identify possible sources. Interestingly, no correlation between sediment and oyster concentrations at the same sites was found. This is supported by completely different contamination patterns, suggesting different sources for both matrices. Hazard assessment revealed possible effects at six out of eight sites on the benthic communities and oyster populations. The contribution of PAH intake via oyster consumption to carcinogenic risks in humans seems to be low.     

Preliminary examination of contaminant loadings in farmed salmon, wild salmon and commercial salmon feed

This pilot study examined five commercial salmon feeds, four farmed salmon (one Atlantic, three chinooks) and four wild salmon (one chinook, one chum, two sockeyes) from the Pacific Coast for PCBs (112 congeners), polybrominated diphenylethers (PBDEs - 41 congeners), 25 organochlorine pesticides (OPs), 20 polycyclic aromatic hydrocarbons (PAHs), and methyl and inorganic mercury. The farmed salmon showed consistently higher levels of PCBs, PBDEs, OPs (except toxaphene) than the wild salmon. The mean concentrations in pg/g were 51,216 vs 5302 for total PCBs; 2668 vs 178 for total PBDEs; 41,796 vs 12,164 for total OPs (except toxaphene). The farmed salmon levels are likely a consequence of the elevated level of contamination found in the commercial salmon feed (mean concentrations in pg/g were 65,535 for total PCBs; 1889 for total BPDEs; 48,124 for total OPs except toxaphene). Except for a single high wild chinook value, PAHs were highest in the feed samples followed by the farmed fish and the three other wild fish. The Bio-Oregon-1996 feed of hatchery origin showed a level of PAHs ten times higher than any other feed. The genotoxic implications of such a high PAH level are considered for juvenile chinook salmon. Toxaphene and methyl mercury concentrations were not notably different between the wild and farmed salmon. There was no clear low contaminant brand of salmon feed. The human health implications of eating farmed salmon are considered from the perspective of the current WHO and Health Canada (2000) tolerable daily intake (TDI) values for PCBs. Based on a TDI of 1 pg TEQ/kg bw/day, this analysis indicated a safety concern for individuals who on a regular weekly basis consume farmed salmon produced from contaminated feed.     

Inorganic arsenic levels in baby rice are of concern

Inorganic arsenic is a chronic exposure carcinogen. Analysis of UK baby rice revealed a median inorganic arsenic content (n = 17) of 0.11 mg/kg. By plotting inorganic arsenic against total arsenic, it was found that inorganic concentrations increased linearly up to 0.25 mg/kg total arsenic, then plateaued at 0.16 mg/kg at higher total arsenic concentrations. Inorganic arsenic intake by babies (4-12 months) was considered with respect to current dietary ingestion regulations. It was found that 35% of the baby rice samples analysed would be illegal for sale in China which has regulatory limit of 0.15 mg/kg inorganic arsenic. EU and US food regulations on arsenic are non-existent. When baby inorganic arsenic intake from rice was considered, median consumption (expressed as μg/kg/d) was higher than drinking water maximum exposures predicted for adults in these regions when water intake was expressed on a bodyweight basis.     

Mixture risk assessment due to ingestion of arsenic,copper, and zinc from milkfish farmed in contaminated coastal areas

Human health risks associated with the consumption of metal-contaminated fish over extended periods have become a concern particularly in Taiwan, where fish is consumed on a large scale. This study applied the interaction-based hazard index (HI) to assess the mixture health risks for fishers and non-fishers who consume the arsenic (As), copper (Cu), and zinc (Zn) contaminated milkfish from As-contaminated coastal areas in Taiwan, taking into account joint toxic actions and potential toxic interactions. We showed that the interactions of As–Zn and Cu–Zn were antagonistic, whereas As–Cu interaction was additive. We found that HI estimates without interactions considered were 1.3–1.6 times higher than interactive HIs. Probability distributions of HI estimates for non-fishers were less than 1, whereas all 97.5%-tile HI estimates for fishers were >1. Analytical results revealed that the level of inorganic As in milkfish was the main contributor to HIs, indicating a health risk posed to consumers of fish farmed in As-contaminated areas. However, we found that Zn supplementation could significantly decrease As-induced risk of hematological effect by activating a Zn-dependent enzyme. In order to improve the accuracy of health risk due to exposure to multiple metals, further toxicological data, regular environmental monitoring, dietary survey, and refinement approaches for interactive risk assessment are warranted.     

Nationwide monitoring of mercury in wild and farmed fish from fresh and coastal waters of Korea

Mercury (Hg) concentrations were monitored in wild and cultured fish collected from fresh and coastal waters in the Korean peninsula from April 2006 to August 2008 nationwide. Total Hg concentrations were reported for 5043 fish samples, including 78 species from 133 locations. Significant interspecies variation was noted in the Hg levels. The average Hg concentration in each fish species ranged from 6.31 μg kg⁻¹ for mullet (Mugil cephalus) to 200 μg kg⁻¹ for mandarin fish (Siniperca scherzeri). Among the species collected, the maximum concentration of Hg, 1720 μg kg⁻¹, was measured in an Amur catfish (Silurus asotus). Only wild freshwater fish exceeded the WHO ingestion standard. Wild freshwater piscivorous fish samples from a large artificial upstream lake contained the highest Hg levels. Hg concentrations were compared between fish groups categorized as wild and farmed fish from freshwater and coastal waters. Although the wild freshwater fish had similar size ranges, their Hg concentrations were higher than those of the other groups. Compared to the feed of farmed marine and freshwater fishes, the prey of wild freshwater fish had a higher Hg concentration, and the total Hg concentrations in freshwater and associated sediment samples were higher than those in coastal water and associated sediment samples. In the freshwater environment, piscivorous fish bioaccumulated two times more Hg than carnivorous and omnivorous fish and four times more than planktivorous fish. The difference in Hg concentrations among trophic groups might have been due to differences in the size of fish, in addition to the variations among different trophic groups. These data will be useful for developing the fish consumption advisory as a management measure to reduce Hg exposure.     

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning,bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 L kg^?1) than in EST (55 L kg^?1), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.     

Heavy metals and metalloids in egg contents and eggshells of passerine birds from Arizona

Concentrations of inorganic elements were determined in eggs of passerine birds including the endangered southwestern willow flycatcher (Empidonax traillii extimus) from four regions in Arizona. The main aim of the study was to determine the distribution of metals in egg contents and eggshells, with emphasis on the deposition of Sr in eggshells. Seventy eggs of 11 passerine species were collected at four nesting locations during 2000. Aluminum, Ba, Cr, Cu, Mn, Se, Sr, and Zn, were detected primarily in egg contents of all bird species. Arsenic, Ni, Pb, and V were detected primarily in eggshells. A proportion of most inorganic elements accumulated in the eggshell. Concentrations of Ba, Cu, Mn, Se, Sr, and Zn in egg contents and As, Ba, Cu, and V in eggshells of yellow-breasted chats (Icteria virens) were similar among locations. However, concentrations of Mn, Ni, Sr, and Zn in eggshells were significant different among locations. Except for Cu, Mn, Se, and Zn, concentrations of inorganic elements were 2-35 times greater in eggshells than in eggs. Most concentrations of metals and metalloids in eggs and eggshells of all the bird species were below levels known to affect reproduction or that have other deleterious effects. However, I found somewhat elevated concentrations of Sr in eggshells (highest MEAN=1505 microg/g dw, n=3) of yellow-breasted chats and willow flycatchers, and in egg contents of yellow warblers (Dendroica petechia) and song sparrows (Melospiza melodia). Whether current observed concentrations of Sr in eggshells are affecting nesting birds in Arizona remains to be determined. Strontium and other metals could be associated with lower hatching success in some areas. This study shows that a proportion of many inorganic elements accumulates in the eggshell and that the potential effects on the proper structure and functioning of the eggshell should not be ignored.     

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Total and inorganic arsenic in Antarctic macroalgae

The Antarctic region offers unparalleled possibilities of investigating the natural distribution of metals and metalloids, such as arsenic. Total and inorganic As were analysed in nine species of Antarctic macroalgae collected during the 2002 summer season in the Potter Cove area at Jubany-Dallmann Station (South Shetland Islands, Argentinian Base). Total As was determined by inductively coupled plasma-optical emission spectrometry after microwave-assisted acid digestion. Inorganic As was determined by acid digestion, solvent extraction, flow injection-hydride generation-atomic absorption spectrometry. Total As ranged from 5.8 microg g(-1) dry weight (dw) (Myriogramme sp.) to 152 microg g(-1)dw (Himantothallus grandifolius). Total As concentrations were higher in Phaeophytes (mean+/-SD: 71+/-44 microg g(-1)dw) than in Rhodophytes (mean+/-SD: 15+/-11 microg g(-1)dw). Inorganic As ranged from 0.12 microg g(-1) (Myriogramme sp.) to 0.84 microg g(-1)dw (Phaeurus antarcticus). The percentage of inorganic As with respect to total As was 0.7 for Phaeophytes, but almost 4 times higher for Rhodophytes (2.6). The work discusses possible causes for the presence of As in marine organisms in that pristine environment.     

Depuration of copper and zinc by green oysters and blue mussels of Taiwan

This paper describes depuration processes of copper and zinc in green oysters (Crassostrea gigas) and in blue mussels (Mytilus smarangdium) collected from an environment with heavy copper contamination, and then transferred to natural clean seawater. Results show that the total loss of copper content per oyster is an exponential function of exposure time for the first 6 days with a depuration rate of 351 microg g(-1) day(-1) and then levels off. During this exponential decrease period approximately 67% of the copper accumulated in green oysters was depurated. However, when the copper contents in the oysters decreased from 2225 +/- 111 microg g(-1) to 344 +/- 18.7 microg g(-1) the depuration rates decreased from 245 microg g(-1) day(-1) to 0.08 microg g(-1) day(-1). This means that green oysters had a 16-fold higher copper depuration rate (351 microg g(-1) day(-1)) than normal oysters (21.5 microg g(-1) day(-1)) for the first 6 days. However, the depuration of accumulated copper and zinc by the mussels was a fast process in natural clean seawater. About 91% of the accumulated copper was lost during the first 6-day period; copper contents declined from 20.2 +/- 3.41 microg g(-1) to 1.80 +/- 0.21 microg g(-1). Only 36% of the accumulated zinc was lost during a depuration period of 6 days. Calculations show that the biological half-lives of copper in green and normal oysters were 11.6 and 25.1 days, respectively. The biological half-lives of zinc in green and normal oysters were 16.7 and 30.1 days, respectively. In spite of the relatively low initial copper content in blue mussels being 20.2 +/- 3.41 microg g(-1), the biological half-life is only 6.40 days. From these results it is important to emphasise that the fastest turnover rate is for copper in blue mussels. However, zinc is more retentive in blue mussels than copper.     

Speciated arsenic in air: measurement methodology and risk assessment considerations

Accurate measurement of arsenic (As) in air is critical to providing a more robust understanding of arsenic exposures and associated human health risks. Although there is extensive information available on total arsenic in air, less is known on the relative contribution of each arsenic species. To address this data gap, the authors conducted an in-depth review of available information on speciated arsenic in air. The evaluation included the type of species measured and the relative abundance, as well as an analysis of the limitations of current analytical methods. Despite inherent differences in the procedures, most techniques effectively separated arsenic species in the air samples. Common analytical techniques such as inductively coupled plasma mass spectrometry (ICP-MS) and/or hydride generation (HG)- or quartz furnace (GF)-atomic absorption spectrometry (AAS) were used for arsenic measurement in the extracts, and provided some of the most sensitive detection limits. The current analysis demonstrated that, despite limited comparability among studies due to differences in seasonal factors, study duration, sample collection methods, and analytical methods, research conducted to date is adequate to show that arsenic in air is mainly in the inorganic form. Reported average concentrations of As(III) and As(V) ranged up to 7.4 and 10.4 ng/m3, respectively, with As(V) being more prevalent than As(III) in most studies. Concentrations of the organic methylated arsenic compounds are negligible (in the pg/m3 range). However because of the variability in study methods and measurement methodology, the authors were unable to determine the variation in arsenic composition as a function of source or particulate matter (PM) fraction. In this work, the authors include the implications of arsenic speciation in air on potential exposure and risks. The authors conclude that it is important to synchronize sample collection, preparation, and analytical techniques in order to generate data more useful for arsenic inhalation risk assessment, and a more robust documentation of quality assurance/quality control (QA/QC) protocols is necessary to ensure accuracy, precision, representativeness, and comparability.     

Inorganic arsenic and trace elements in Ghanaian grain staples

A total of 549 samples of rice, maize, wheat, sorghum and millet were obtained from markets in Ghana, the EU, US and Asia. Analysis of the samples, originating from 21 countries in 5 continents, helped to establish global mean trace element concentrations in grains; thus placing the Ghanaian data within a global context. Ghanaian rice was generally low in potentially toxic elements, but high in essential nutrient elements. Arsenic concentrations in rice from US (0.22 mg/kg) and Thailand (0.15 mg/kg) were higher than in Ghanaian rice (0.11 mg/kg). Percentage inorganic arsenic content of the latter (83%) was, however, higher than for US (42%) and Thai rice (67%). Total arsenic concentration in Ghanaian maize, sorghum and millet samples (0.01 mg/kg) was an order of magnitude lower than in Ghanaian rice, indicating that a shift from rice-centric to multigrain diets could help reduce health risks posed by dietary exposure to inorganic As.     

Contribution of Nitrate and Carbonaceous Species to PM2.5 Observed in Canadian Cities

ABSTRACT

At a variety of Canadian monitoring sites, carbonaceous compounds were estimated to account for an average of 50% of fine particle mass. These estimates were determined by subtracting the total fine particle mass associated with inorganic compounds from the total fine mass determined gravimetrically. This approach, which yields an upper limit estimate of the total amount of carbon-related mass was necessary since particulate carbon was not measured in the Canadian National Air Pollution Surveillance (NAPS) network. In this paper, total carbon estimates are evaluated against organic and elemental carbon measurements at locations in the Greater Vancouver area and Toronto. In addition, particle nitrate measurements at seven Canadian locations are used to determine the importance of nitrate relative to total mass and to examine the sampling artifacts due to the loss of particle nitrate from Teflon filters used in the NAPS di-chotomous samplers.

Measurements of organic and elemental carbon indicated that the total carbon estimation approach provides representative estimates of the average contribution by carbonaceous material to the total fine and coarse mass. The average total carbon among all Vancouver area measurements (N = 225) was 4.28 μg m^-3, while the estimated value was 4.34 μg m^-3. There was a larger discrepancy between Toronto total carbon measurements (12.1 μg m^-3) and estimates (8.8 μg m^-3), which is attributed in part to sampling of particles above 10 mm in diameter. However, the R² relating the measurements and estimates was about 0.71 for both areas. Linear regression slopes of 0.98 for Vancouver and 0.78 for Toronto (nonsignificant intercepts) indicate little bias in the Vancouver estimates, but a tendency for underestimation as the observed total carbon concentration increased in Toronto.

Annually, nitrate was responsible for 17% and 12% of the fine mass in the Vancouver area and Ontario, respectively. In contrast, at two rural locations in southern Quebec and Nova Scotia, only 6% of fine mass was associated with nitrate. Due to filter losses, nitrate concentrations determined through the NAPS dichot sampling were much lower than actual concentrations (0.44 μg m^-3 vs. 2.63 μg m^-3). As a result of these losses (attributed mostly to loss during laboratory storage), previous total carbon estimates for the Canadian NAPS sites were likely to have been overestimated on average by about 10%.