The impact of a rice based diet on urinary arsenic

Rice is elevated in arsenic (As) compared to other staple grains. The Bangladeshi community living in the United Kingdom (UK) has a ca. 30-fold higher consumption of rice than white Caucasians. In order to assess the impact of this difference in rice consumption, urinary arsenicals of 49 volunteers in the UK (Bangladeshi n = 37; white Caucasians n = 12) were monitored along with dietary habits. Total urinary arsenic (As(t)) and speciation analysis for dimethylarsinic acid (DMA), monomethylarsonic acid (MA) and inorganic arsenic (iAs) was conducted. Although no significant difference was found for As(t) (median: Bangladeshis 28.4 μg L(-1)) and white Caucasians (20.6 μg L(-1)), the sum of medians of DMA, MA and iAs for the Bangladeshi group was found to be over 3-fold higher (17.9 μg L(-1)) than for the Caucasians (3.50 μg L(-1)). Urinary DMA was significantly higher (p < 0.001) in the UK Bangladeshis (median: 16.9 μg DMA L(-1)) than in the white Caucasians (3.16 μg DMA L(-1)) as well as iAs (p < 0.001) with a median of 0.630 μg iAs L(-1) for Bangladeshi and 0.250 μg iAs L(-1) for Caucasians. Cationic compounds were significantly lower in the Bangladeshis (2.93 μg L(-1)) than in Caucasians (14.9 μg L(-1)). The higher DMA and iAs levels in the Bangladeshis are mainly the result of higher rice consumption: arsenic is speciated in rice as both iAs and DMA, and iAs can be metabolized, through MA, to DMA by humans. This study shows that a higher dietary intake of DMA alters the DMA/MA ratio in urine. Consequently, DMA/MA ratio as an indication of methylation capacity in populations consuming large quantities of rice should be applied with caution since variation in the quantity and type of rice eaten may alter this ratio.     

Quantitative arsenic speciation in two species of earthworms from a former mine site

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.     

Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS)

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'.     

Arsenic exposure in Hungary, Romania and Slovakia

Inorganic arsenic is a potent human carcinogen and toxicant which people are exposed to mainly via drinking water and food. The objective of the present study was to assess current exposure to arsenic via drinking water in three European countries. For this purpose, 520 individuals from four Hungarian, two Slovakian and two Romanian countries were investigated by measuring inorganic arsenic and methylated arsenic metabolites in urine by high performance liquid chromatography with hydride generation and inductively coupled plasma mass spectrometry. Arsenic in drinking water was determined by atomic absorption spectrometry. Significantly higher concentrations of arsenic were found in both the water and the urine samples from the Hungarian counties (median: 11 and 15 microg dm(-3), respectively; p < 0.001) than from the Slovakian (median: 0.94 and 4.5 microg dm(-3), respectively) and Romanian (median: 0.70 and 2.1 microg dm(-3), respectively) counties. A significant correlation was seen between arsenic in water and arsenic in urine (R(2)= 0.46). At low water arsenic concentrations, the relative amount of dimethylarsinic acid (DMA) in urine was increased, indicating exposure via food. Also, high body mass index was associated with higher concentrations of arsenic in urine (p= 0.03), mostly in the form of DMA. Smokers had significantly higher urinary arsenic concentrations than non-smokers (p= 0.03). In conclusion, elevated arsenic exposure via drinking water was prevalent in some of the counties. Exposure to arsenic from food, mainly as DMA, and cigarette smoke, mainly as inorganic arsenic, are major determinants of arsenic exposure at very low concentrations of arsenic in drinking water.     

Airborne exposure and biological monitoring of bar and restaurant workers before and after the introduction of a smoking ban

The aims were to assess the impact of a total smoking ban on the level of airborne contaminants and the urinary cotinine levels in the employees in bars and restaurants. In a follow up design, 13 bars and restaurants were visited before and after the implementation of a smoking ban. Ninety-three employees in the establishments were initially included into the study. The arithmetic mean concentration of nicotine and total dust declined from 28.3 microg m(-3) (range, 0.4-88.0) and 262 microg m(-3) (range, 52-662), respectively, to 0.6 microg m(-3) (range, not detected-3.7) and 77 microg m(-3) (range, not detected-261) after the smoking ban. The Pearson correlation coefficient between airborne nicotine and total dust was 0.86 (p < 0.001; n = 48). The post-shift geometric mean urinary cotinine concentration declined from 9.5 microg g(-1) creatinine (cr) (95% CI 6.5-13.7) to 1.4 microg g(-1) cr (95% CI 0.8-2.5) after the ban (p < 0.001) in 25 non-snuffing non-smokers. A reduction from 1444 microg g(-1) cr (95% CI 957-2180) to 688 microg g(-1) cr (95% CI 324-1458) was found (p < 0.05) in 29 non-snuffing smokers. The urinary cotinine levels increased from 11.7 microg g(-1) cr (95% CI 7.0-19.6) post-shift to 21.9 microg g(-1) cr (95% CI 13.3-36.3) (p < 0.01) in the next morning in 24 non-snuffing non-smokers before the smoking ban. A substantial reduction of airborne nicotine and total dust was observed after the introduction of a smoking ban in bars and restaurants. The urinary cotinine levels were reduced in non-smokers. The decline found in smokers may suggest a reduction in the amount of smoking after intervention. In non-smokers cotinine concentrations were higher based on urine sampled the morning after a shift than based on urine sampled immediately post-shift.     

Determination of germanium in urine and its usefulness for biomonitoring of inhalation exposure to inorganic germanium in the occupational setting

The present study aimed to assess whether urinary germanium concentration can be used as a biomarker of inhalation exposure to airborne dust from metallic germanium (Ge) or GeO2 in the occupational setting. A novel hydride generation-based method coupled with fow-injection graphite furnace atomic absorption spectrometry (HG/FI-GFAAS) was developed for the determination of urinary germanium. It was found that urinary germanium concentration could be reliably determined by a standard additions method after thorough digestion of the urine and careful pH adjustment of the digest. The limit of detection (LOD) in urine for the HG/FI-GFAAS method was 0.25 microg Ge L(-1). In Belgian control male subjects, the urinary germanium concentration was below this LOD. In 75 workers currently exposed to inorganic germanium compounds, respirable and inhalable concentrations of germanium in the aerosols were measured on Monday and Friday at the job sites using personal air samplers. Spot-urine samples were collected on the same days before and after the work shift. The germanium concentrations of respirable dust correlated very well with those of inhalable dust and represented 20% of the inhalable fraction. Workers exposed to metallic Ge dust were on average ten times less exposed to germanium than those whose exposure involved GeO2 (3.4 versus 33.8 microg Ge m(-3)). This difference was reflected in the urinary germanium concentrations (3.4 versus 23.4 microg Ge g(-1) creatinine). Regression analysis showed that the concentration of germanium in the inhalable fraction explained 42% of the post-shift urinary germanium concentration either on Monday or on Friday, whereas in a subgroup of 52 workers mainly exposed to metallic germanium dust 57% (r = 0.76) of the Monday post-shift urinary germanium was explained. Urinary elimination kinetics were studied in seven workers exposed to airborne dust of either metallic Ge or GeO2. The urinary elimination rate of germanium was characterised by half-times ranging from 8.2 to 18.1 h (on average 12 h 46 min). The present study did not allow discrimination between the germanium species to which the workers were exposed, but it showed fast urinary elimination kinetics for inhalation exposure to dust of metallic Ge and GeO2. It pointed out that urine samples taken at the end of the work shift can be used for biological monitoring of inorganic germanium exposure in the occupational setting.     

Environmental monitoring of historical change in arsenic deposition with tree bark pockets

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.     

Population-based biomonitoring in the Czech Republic: urinary arsenic

The method of Guo et aL (AnaL Chim. Acta, 1997, 349, 313-318) for the determination of the toxicologically relevant arsenic in urine was verified and then used for the determination of arsenic in urine of the Czech population for monitoring purposes. Statistical evaluation at the level alpha = 0.05 did not prove any significant differences between industrial and agricultural regions, between males and females and smokers and nonsmokers. Likewise no differences were found among children in all the regions monitored. In the adult population small differences were found between some regions but these differences were not dependent on industrial pollution. The values of toxicologically relevant arsenic are low for all regions. The summarised value of the median for all groups together is 3.5 microg (g creatinine)(-1).     

Inorganic arsenic levels in rice milk exceed EU and US drinking water standards

Under EU legislation, total arsenic levels in drinking water should not exceed 10 microg l(-1), while in the US this figure is set at 10 microg l(-1) inorganic arsenic. All rice milk samples analysed in a supermarket survey (n = 19) would fail the EU limit with up to 3 times this concentration recorded, while out of the subset that had arsenic species determined (n = 15), 80% had inorganic arsenic levels above 10 microg l(-1), with the remaining 3 samples approaching this value. It is a point for discussion whether rice milk is seen as a water substitute or as a food, there are no EU or US food standards highlighting the disparity between water and food regulations in this respect.     

Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

Urinary 8-hydroxy-2'-deoxyguanosine in inhabitants chronically exposed to arsenic in groundwater in Cambodia

Arsenic concentrations in hair and urine, and urinary levels of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a marker of oxidative DNA damage, were examined for inhabitants of the Mekong Basin in Kratie Province, Cambodia. Also, the arsenic levels of tube-well water were determined. Total arsenic concentrations in tube-well water ranged from <1 to 886 microg L(-1), and 44.8% of these exceeded the WHO drinking water guideline of 10 microg L(-1). Elevated levels of arsenic were observed in the human hair and urine, and also a significant positive correlation was observed between the concentrations in hair and urine. These results suggest that the inhabitants are chronically exposed to arsenic through drinking the tube-well water. Levels of urinary 8-OHdG were higher for the subjects with higher arsenic levels in hair and urine, suggesting that induction of oxidative DNA damage was caused by chronic exposure to arsenic in tube-well water for the inhabitants in Kratie Province. To our knowledge, this is the first report on the oxidative DNA damage caused by chronic exposure to arsenic in groundwater for the inhabitants in Cambodia.     

Application of natural zeolites for preconcentration of arsenic species in water samples

Zeolites of the clinoptilolite type produced in Mexico and Hungary were investigated with respect to their sorption efficiency for various redox species of arsenic. Long-term experiments showed that arsenate remains stable for a long period in spiked deionised water and drinking water, as well as in the surface water of the Biela valley in Saxony, Germany. Both clinoptilolites are able to decrease the initial arsenic concentration of 200 microg l(-1) by more than 75% in deionised, drinking, ground and surface waters. In the case of the Mexican zeolite, both the arsenite and the arsenate concentrations (200 microg l(-1)) can be lowered from 200 microg l(-1) to 10 microg l(-1), which is the World Health Organisation's (WHO's) recommended maximum level. It was found that the presence of cations and anions in the natural waters of Biela, Germany, and Zimapán, Mexico, did not reduce the efficiency of the selected zeolites. The Hungarian zeolite removed 75% of the arsenate in the Zimapán water and only 50% when the sample was first acidified. This zeolite totally desorbed the fixed arsenic into a water volume that was half the volume in the adsorption experiment.     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Multi-component assessment of worker exposures in a copper refinery. Part 1. Environmental monitoring

The exposure characterisation described in this paper for 135 copper refinery workers (45 females, 90 males) focuses on the concentrations of copper, nickel and other trace elements in the inhalable aerosol fractions, as well as in the water-soluble and water-insoluble subfractions. Some information is also provided on the thoracic and respirable aerosol fractions. Further, results are presented for volatile hydrides of arsenic and selenium released in the copper purification steps of the electrorefining process. For the pyrometallurgical operations, a comparison of the geometric means for the inhalable aerosol fraction indicated that water-soluble copper levels were on average 19-fold higher compared to nickel (p < 0.001) and a significant association was evident between them (r = 0.87, p < 0.001); for the insoluble subfraction, the copper : nickel ratio was 12.5 (p < 0.001) and the inter-element correlation had r = 0.98 and p < 0.001. Although for the electrorefinery workers the relative inhalable concentrations of copper and nickel were not significantly different (p > 0.05), the corresponding inter-element associations were: slope of 7.7, r= 0.54, p < or =0.001 for the water-soluble subfraction and slope of 1.3, r = 0.71 and p < or =0.001 for the water-insoluble subfraction. On average, a good proportion of the inhalable copper and nickel were found in the thoracic (40%) and respirable (20%) aerosol fractions. Cobalt air concentrations were generally low with geometric means and 95% confidence intervals of 3.1 (2.4-4.2)microg m(-3) (pyrometallurgical workers) and 0.3 (0.4-0.5) microg m(-3)(electrorefinery workers). Similarly, the maximum concentrations of cadmium and lead were low, respectively 4 and 25 microg m(-3). Of the hydrides, tellurium and antimony could not be detected, but for the arsenic (arsine) and selenium hydrides measurable exposure occurred for almost all electrorefinery workers, although the levels were generally low at 0.2 microg m(-3).     

Correlation of urinary nickel excretion with observed 'total' and inhalable aerosol exposures of nickel refinery workers

An investigation of the relationship between observed nickel aerosol exposures and urinary nickel excretion was undertaken at a Scandinavian nickel refinery. The goal of the study was to assess the impact of nickel aerosol speciation, the use of particle size-selective sampling instrumentation and adjustment of urinary levels for creatinine excretion on the usefulness of urinary nickel excretion as a marker for exposure. Urinary nickel measurements and paired 'total' and inhalable aerosol exposure measurements were collected each day for one week from refinery workers in four process areas. The mean observed urinary nickel concentration was 12 micrograms L-1 (11 micrograms of Ni per g of creatinine). The strongest relationships between urinary excretion and aerosol exposure were found when urinary nickel levels were adjusted for creatinine excretion and when exposure to only soluble forms of nickel aerosol was considered. No significant difference was observed between measures of 'total' and inhalable aerosol in the ability to predict urinary excretion patterns. In the light of these results, it is recommended that consideration be given to the chemical species distribution of nickel aerosol in the use of urinary nickel measurements as a screening tool for cancer risk in occupationally-exposed populations.     

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry

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.     

Methylated arsenic, antimony and tin species in soils

Methylated species of antimony, arsenic and tin were examined in urban soils of the Ruhr basin, near the cities of Duisburg and Essen, Germany. The main aim of this study was to investigate the occurrence of mono-, di- and trimethylated species of these elements in urban soils. The influence of historical and present land use upon the species content was examined. The distribution of inorganic As, Sb and Sn and their methylated species along the profile depth was investigated. As, Sb and Sn speciation was performed by pH-gradient hydride generation purge and trap gas chromatography, followed by inductively-coupled plasma mass spectrometry (HG-PT-GC/ICP-MS). Species' structures were confirmed by GC-EI/MS-ICP-MS. Monomethylated Sb and As were the dominant species detected: the concentration of these metal(loid) species varied between <0.07-56 microg kg(-1) per dry mass. All dimethylated species and monomethyltin concentrations were between <0.01-7.6 microg kg(-1) per dry mass, and for the trimethylated species of all examined elements, concentrations between <0.001-0.63 microg kg(-1) per dry mass were detected. The highest organometal(loid) concentrations were observed in agricultural soils and garden soils; lower concentrations were found in the soils of abandoned industrial sites (wasteland, primary forest and grassland) and a flood plain soil of the Rhine. This result can be ascribed to both the cultivation and the increased biological activity of the agricultural soils, and the generally higher contamination, the disturbed structure and the artificial substrates (deposits from industrial sources) of the abandoned industrial soils. Due to periodical sedimentation, the flood plain profile was the only one where no depth dependence of organometal(loid) species concentration was detected. The other soil profiles showed a decrease of species content with increasing depth; this was particularly noticeable in soils with a clear change from a horizon with an organic character towards a mineral horizon, i.e. decreasing vitality from profile top to bottom. It is not as yet clear whether the organometal(loid) species are formed in the mineral horizons of the profiles or whether they are displaced from the organic, biologically-active horizons towards the mineral horizons. Field studies revealed that soil parameters like pH, water content or temperature did not correlate significantly with the degree of biomethylation observed. In contrast to the lower in vitro biomethylation efficiency of Sb vs. As in microbial incubations, we consistently detected higher proportions of transformed Sb compounds in situ in soil samples. These data may indicate a need to re-examine the currently accepted model of Sb biogeochemical cycling in the real environment.     

Time trend of Butyl- and Phenyl-Tin contamination in organisms of the Lagoon of Venice (1999–2003)

In the period 1999-2003 a monitoring study on the accumulation of organotin compounds in edible organisms in the Lagoon of Venice was conducted. Butyl and Phenyl derivatives were determined in pooled samples of Mytilus galloprovincialis and Tapes spp. with the aims of assessing organotin contamination in the Lagoon of Venice in the period just preceding their ban in Europe, monitoring the concentrations in organisms with a high commercial use, evaluating a potential hazard for human health due to seafood and identifying the possible contamination sources. Sampling stations (up to 20) were distributed around the Lagoon and particularly concentrated in the area close to the town of Chioggia. Significantly higher (analysis of variance (ANOVA), p < 0.05) tributyltin (TBT) concentrations were found in mussels (from 38 +/- 8 to 6,666 +/- 1,333 microg kg(-1) d.w., as TBT(+)), than in clams (from 6 +/- 1 to 2,256 +/- 451 microg kg(-1) d.w., as TBT(+)). During the 3 years of the survey no increase in average concentrations of the butyltin compounds (tributyltin (TBT) + dibutyltin (DBT) + monobutyltin (MBT)) was observed (ANOVA, p > 0.05) in either species. Furthermore, by analyzing the entire data set, it is evident that most stations show analogous concentrations in the 3 years for both species, whereas few have anomalously higher concentrations. If organotin concentrations in specimens from some sites are compared with the Tolerable Average Residue Level, a possible risk for human health must be considered.     

Biomonitoring of tin and arsenic in different compartments of a limnic ecosystem with emphasis on Corbicula fluminea and Dikerogammarus villosus

Asian clam Corbicula fluminea, the amphipod Dikerogammarus villosus and the macrophyte Nuphar lutea were tested for investigating spatial and temporal variability in the bioavailability of tin and arsenic in the River Lippe, Germany. Samples were collected from September 2002 to May 2003 at a tin polluted site (source pollution) and a reference site. Additional screening sampling was carried out twice in April 2003 to test the extent of As and Sn concentration in periphyton (aufwuchs) samples. Accumulated Sn and As concentrations were measured with ICP-MS after sample processing (dissection, cryo-milling) and digestion. Quality control was performed by parallel analysis of three certified reference materials. Measurable As and Sn contents in plant tissues were only detectable in roots (below 30 microg kg(-1) and 20 microg kg(-1) for As and Sn, respectively). Homogenates from C. fluminea and D. villosus tissues showed site-dependent trace metal contents. Elevated bioavailability of Sn is present downstream of the sewage discharge of the world's biggest producer of tributyltin (TBT) at Luenen (northern Ruhr region). In comparison to C. fluminea, D. villosus shows higher concentrations of tin in samples from both sites. Arsenic concentrations in C. fluminea remain constant with increasing shell size, whereas tin shows a size-dependent accumulation. The results indicate that Corbicula fluminea and Dikerogammarus villosus are suitable passive biomonitoring organisms for Sn, but As levels might be actively regulated. The concentration of tin in the periphyton (aufwuchs) samples was found to be much higher in samples from a contaminated site (428 +/- 63 vs. 1949 +/- 226 microg kg(-1)).