Liquid chromatography-hydride generation-atomic absorption spectrometry for the speciation of tin in seafoods

Liquid chromatography with hydride generation atomic absorption spectrometry as the detection system was applied to the separation and determination of inorganic tin, tributyltin, dibutyltin, monobutyltin, diphenyltin and monophenyltin. A reversed phase C18 column and a methanol/water/acetic acid (70:27:3, v/v/v) mixture containing 0.05%(v/v) triethylamine and 0.1%(w/v) tropolone as the mobile phase (isocratic elution) were used. Extraction of organotins from the samples was carried out using methanol containing 0.05%(w/v) tropolone, a process that was repeated twice. The supernatants were shaken with water and dichloromethane in a separating funnel and the organic phase was collected and evaporated to dryness. When the method was applied to the speciation of tin in fresh and canned mussels, no organotins above the detection limits were identified in any of the samples, inorganic tin being the only species detected. The reliability of the procedure was checked by analyzing the total tin content of the samples by electrothermal atomic absorption spectrometry and by speciation of tin in a certified reference material, mussel tissue (CRM 477). The method can be used for environmental monitoring of organotins contaminated samples.     

Organotin compounds in surface sediments from seaports on the Gulf of Gda??sk (southern Baltic coast)

Sediment samples were collected in two Polish ports of international significance--the Port of Gdańsk and the Port of Gdynia (Gulf of Gdańsk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdańsk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.     

Monitoring of organotin compounds in seawater using semipermeable membrane devices (SPMDs)--tentative results

The impact of anthropogenic pollutants on the marine ecosystem is related to the concentrations experienced by the biota in the seawater and the resulting concentration in the organism. Results from monitoring of pollutants in water samples provide snapshots that can be high or low depending on a wide range of variables. To provide more integrated information, semipermeable membrane devices, SPMDs, have been used to monitor different organic pollutants. In this survey, SPMDs were used to monitor organotin compounds in the marine environment. Time-integrated sampling using SPMDs and direct water sampling was carried out at six stations in the inner Oslofjord, Norway. The sample work-up procedure for both water and SPMDs was based on direct derivatisation using NaBEt4 and simultaneous extraction with an organic solvent. Analysis was performed using a gas chromatograph equipped with an atomic emission detector. The results show that SPMDs do accumulate organotin compounds from the water phase. Both tributyl- (TBT) and dibutyltin were detected in all of the analysed membranes while no monobutyltin was found. Levels found in SPMDs range from < 1 to 220 ng Sn SPMD(-1). Water concentrations range from 0.4 to 10 ng Sn L(-1). An investigation of relative levels of TBT showed a similar concentration gradient in the inner Oslofjord using either direct water sampling or passive sampling by SPMDs. As the membranes are able to accumulate the organotins from the water it will be possible to locate lower concentrations than with direct analyses of water samples.     

Organotin compounds in a Norwegian fjord. A comparison of concentration levels in semipermeable membrane devices (SPMDs), blue mussels (Mytilus edulis) and water samples

Monitoring concentrations of organic pollutants in water is essential to predict effects and to initiate preventive steps. Results from the analysis of water samples provide snapshots of a situation, whereas monitoring using semipermeable membrane devices (SPMDs) provides a time-integrated picture of the concentration of pollutants in water. In this investigation, SPMDs, caged mussels and water samples were used to monitor the levels of organotin compounds in the inner Oslofjord, Norway, over a period of 12 weeks. The work-up procedure for the analysis of organotins was optimised, focusing on the clean-up procedure using gel permeation chromatography (GPC). By using several GPC columns, as much as 1 g of triolein could be employed. This reduces the background emission noise on the baseline, leading to an improvement in the detection limits. The main uptake of tributyltin (TBT) in mussels and SPMDs levelled off after 14 days. A longer uptake period was indicated for SPMDs at stations with a high water concentration of TBT (5-10 ng Sn L(-1)) compared with those with a low water concentration of TBT (approximately 1 ng Sn L(-1)). A concentration gradient was observed for water, SPMDs and mussels from the innermost station close to Oslo harbour to the station further out in the fjord, indicating that the three analysed matrices give approximately the same pollution gradient. The bioconcentration factor (BCF) for TBT in mussels was in the range 12-14 000 (wet weight) and, for SPMDs, 10-12 000 (fat). A good correlation with the TBT water concentrations was achieved within a period of 14-30 days of exposure for mussels and after 2-3 months for SPMDs. A good correlation was also found between the TBT concentration in SPMDs and mussels at the end of the experiment. SPMDs can therefore be used to predict concentrations of TBT in both water and mussels.     

Occurrence of organotins in the Yangtze River and the Jialing River in the urban section of Chongqing, China

The occurrence of organotins in the Yangtze River and the Jialing River in the urban section of Chongqing, China and their impact on drinking water waterworks are reported in this study. Water samples were extracted by solid-phase microextraction and measured using a gas chromatograph with mass spectrometer. The results showed that the rivers studied were polluted by both butyltins and phenyltins and that the butyltin species was the dominant pollutant. Butyltins, especially monobutyltin, were detected in all 18 sampling stations, and phenyltins were detected only in 11 sampling stations. Majority of the organotins were MBTs with concentrations varying from 27.3 to 1,145.8 ng Sn L^?1. Diphenyltin and dibutyltin were the second most common with the highest levels of 113.7 and 202.5 ng Sn L^?1, respectively. Monophenyltin, tributyltin, and triphenyltin had the lowest detection rates with concentration levels of 9.7, 161.8, and 37.2 ng Sn L^?1, respectively. Some of the organotins were also detected in drinking water waterworks, which posed a threat to the water quality of Chongqing.     

Depositional profiles and relationships between organotin compounds in freshwater and estuarine sediment cores

A range of organotin compounds including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in sediment cores collected from contaminated freshwater and estuarine sites in Essex and Suffolk, U.K. Butyltin compounds were found in significant quantities at depths of up to 60 cm within the sediments of marina and boatyard complexes with TBT concentrations ranging from <3 ng g^–1 (the detection limit) to >3000 ng g^–1. In general sediment TBT concentrations decreased with depth, but maximum enrichment tended to occur just below the surface. It was evident from these core profiles that the accumulation of organotins in surface deposits was on the decline and coincided approximately, with the implementation in 1987 of the UK retail ban on the sale of TBT based antifouling paints for application on vessels <25 m in length. The degradation rate for TBT in sediments was found to exhibit first order kinetics with half lives ranging from 0.9–5.2 years between different sites. Estimated degradation rates have also been determined for DBT and MBT. These ranged from 1.5–3.0 years for DBT and 1.8–3.7 years for MBT.     

Metals and organotins in multiple bivalve species in a one-off global survey

The Galathea 3 expedition circumnavigated the globe in 2006-2007 and collected marine samples from six continents. Bivalves were collected from harbours, other impacted locations and reference sites, and samples from 57 sites were analyzed for metals and 47 for organotins, to assess current contamination levels on a global scale. Metal concentrations in nine bivalve species were normalised to the Mytilidae family using conversion factors based on cosampled species and literature bioconcentration factors. The lowest metal and tributyltin concentrations were below background assessment concentrations (BACs) agreed in the Oslo-Paris convention (OSPAR) for the North Sea, and at most harbours the concentrations were orders of magnitude above BACs. The lowest concentrations of Cd and Pb measured here suggest that the BACs should be lower in a worldwide context. The sources of metals were classified according to human impact using principal component analysis. High relative concentrations of Hg, Pb and P were source indicators for industrial activity and land use; Zn, organotins, Cd and Cu for shipping activities, and V for oil spills. Generally the concentration levels at reference sites were low, but not always lower than expected impacted areas. The most contaminated areas were harbours, where especially Copenhagen, St Croix and Sydney, can be considered hotspots of tributyltin as well as a number of metals.     

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.     

Organotin compounds in the marine environment of the Bay of Piran,northern Adriatic Sea

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.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Mercury in rivers in NW England: from rural headwaters to the heartlands of the historic industrial base

Total mercury (T-Hg) concentrations in rivers are described across a rural to urban/industrial and agricultural landscape gradient in NW England. T-Hg ranges between 0.2 and 230 ng L(-1). The regional median was 3.6 ng L(-1) with individual river medians ranging between 1.9 and 8.3 ng L(-1). Median T-Hg concentrations were sometimes moderately higher for the lowland areas and at higher flows. Our estimates suggest that the Ribble estuary receives 9.2 kg y(-1) and the Wyre estuary 0.7 kg y(-1). In order to examine regional inputs from urban/industrial components, regression analysis was undertaken by comparing three types of hydrochemical signature: suspended sediments (SS), which provide a measure of the particulate component, dissolved organic carbon (DOC) that provides an indication of humic/fulvic acids that are part of the organic colloids and strong chelating agents, and boron a marker of sewage effluents and population density. The results show high positive relationships of T-Hg with both SS and DOC, but no relationship with the urban/industrial signal. The regression analysis with T-Hg indicated on average a gradient of 0.33 ng mg(-1) for DOC and 0.2 ng mg(-1) for SS. They indicate the primary importance of a diffuse source of T-Hg. For the upland areas and cleaner river systems, the linkages between T-Hg and DOC were particularly strong, while for the lowland areas, the linkage with SS proved stronger. Analysis of a latter subset of data that partition the SS into organic and inorganic fractions indicated that the T-Hg was primarily linked with the organic fraction. Indeed, multiple regression of T-Hg with DOC and POM reveals gradients similar to other parts of the World.     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

Organotins in a medium-size Mediterranean basin (the Herault River)

This study reports the first assessment of organotin pollution in the Hérault watershed, a medium size Mediterranean basin. Organotin compounds were analyzed in surface waters, wells supplying drinking water and sewage treatment plants (STPs). In surface and ground waters, a background contamination by total organotin compounds has been identified in the range of 0.51 +/- 0.02-71 +/- 2 ng(Sn) L(-1), which is of the same order of magnitude as those observed in other European areas. Organotins were systematically present in STP influents and sludge. Total or partial elimination of organotin compounds from treated wastewater was observed. STP effluents appeared nevertheless to be a non-negligible source of contamination not only of rivers but also of aquifers tapped for drinking water supply.Tributyltin concentration was higher than the maximum allowable concentration proposed by the European Commission in some surface waters and wells supplying drinking water. This could compromise the water resource and have serious and irreversible consequences for the aquatic eco-system. As it was the case for the ban of antifouling paints, a regulatory regime in decreasing point-source emissions of these harmful compounds used in household products might be applied.     

Establishment of a sampling strategy for the use of blue mussels as an indicator of organotin contamination in the coastal environment

The application of the Mussel Watch concept to the assessment of chemical contamination in the coastal environment is still premature, since the relationship between the physiological and ecological aspects of blue mussels and the accumulation of contaminants in their soft tissues remains unclear. We cannot yet directly estimate with known confidence the degree of chemical contamination from the levels of contaminants in the soft tissues of mussels. An understanding of the source and range of variability in the tissue concentrations of contaminants is essential, and the establishment of a biomonitoring sampling strategy to minimize the effect of identified sources of variability is required. The present study was conducted to clarify the characteristics of organotin accumulation in blue mussels under various conditions in Tokyo Bay, and to establish an optimized sampling strategy of mussels as exposure indicators of organotin contamination in Japan. It was clear that the sample number, individual size, spawning activity and vertical habitat were factors causing a variation of tissue concentration. Based on a quantitative estimation of the variability of organotin concentration in mussel tissues under various physiological and natural conditions, we suggest that a composite sample of 30 mussels (3-5 cm in shell length), collected from the infralittoral zone prior to their spawning season, is essential to reduce the variability between individuals and to obtain reproducible analytical values at a sampling site. For monitoring sites where natural blue mussels cannot be collected, an alternative method of transplanting blue mussels from a relatively clean area would be required.     

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.     

Organotins in marine mammals and seabirds from Norwegian territory

An increasing number of studies indicate that marine mammals and some seabirds are exposed to organotins. However, results from northern and Arctic areas are few. Here results from analysis of tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT) and monophenyltin (MPhT) in harbour porpoise (Phocoena phocoena), common seal (Phoca vitulina), ringed seal (Phoca hispida) and glaucous gull (Larus hyperboreus) from Norwegian territory are presented. Relatively high concentrations of DBT, TBT and MBT were observed in muscle, kidney and liver from harbour porpoises caught in northern Norway in 1988, just before restrictions on the use of tributyltin (TBT)(mainly on small boats) were introduced in several European countries. The concentrations in harbour porpoise muscle tissue were reduced significantly 11 years later, possibly as a result of the introduced restrictions. Considerably lower concentrations of butyltins were observed in the seals compared to porpoises. The lowest levels of organotins were found in ringed seals from Spitsbergen, where only traces of dibutyltin (DBT) and monobutyltin (MBT) were observed. Traces of DBT and MBT were also found in some individual glaucous gulls from Bear Island. The sum of the degradation products MBT and DBT in liver samples from all analysed species were generally higher than TBT itself. Triphenyltin (TPhT) was observed in all porpoise samples and in livers of common seals. Also the sum of the degradation products MPhT and DPhT in liver samples from porpoise and common seals were higher than TPhT. No traces of phenyltins were found in ringed seals from Spitsbergen or in glaucous gulls from Bear Island. The limited data available indicate low to moderate exposure to organotins in northern areas (Spitsbergen and Bear Island). Marine mammals are however more exposed further south along the Norwegian Coast.     

有机锡化合物的性质、环境污染来源及测定方法

综述了有机锡化合物的性质 ,并对此类化合物在PVC稳定剂、木材防腐剂、农药、防腐涂料和杀螺贝剂等方面的应用作了简介 ,从而指出其主要的环境污染来源。对环境中有机锡化合物的测定方法作了简单评价。     

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.     

Causes of temporal variability of lead in domestic plumbing systems

Sources of lead in drinking water are primarily lead pipe, lead/tin solder, and brass fixture materials.Lead levels in the water depend upon many solubility factors, such as pH, concentrations of substances such as inorganic carbonate, orthophosphate, chlorine, and silicate, the temperature, the nature of the pipe surface, etc. Physical factors, time, and chemical mass transfer are significant in governing lead levels in nonequilibrium systems. The diameter and length of lead pipe is extremely important, as well as the age and chemical history of the solder and brass fixtures. Analytical variability is not particularly significant relative to between-site and within-site variability. Knowledge of temporal variability at each site is necessary to define a statistically valid monitoring program. An analysis of published data covering repetitive measurements at a given site show that the variability of lead concentration at each site tends to be characterized by the frequent occurrence of spikes. Variability expressed as approximate relative standard deviations tends to be of about 50 to 75% in untreated water, regardless of the mean lead concentration. The distributions are frequently nonnormal for small numbers of samples. Monitoring programs must incorporate controls for the causes of the within-site and between-site variability into their sampling design. The determination of necessary sampling frequency, sample number, and sample volume must be made with consideration of the system variability, or the results will be unrepresentative and irreproducible.     

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'.