Evaluation of environmental levels and biological impact of TBT in Malta (central Mediterranean)

Chemical monitoring for butyltins in bulk seawater, surface microlayer and superficial sediments determined that the two main local sources of marine contamination by tributyltin (TBT) compounds in Malta are ship-repairing dockyards and marinas. In bulk seawater, TBT values ranged from below the detection limit of 5 ng Sn l(-1) to 300 ng Sn l(-1); in sediments derived from the most polluted areas, TBT concentrations as high as 1500 ng Sn g(-1) were measured. At TBT levels found in local harbours, several sublethal biological responses are possible and were observed, including a significant reduction in MFO enzyme system activities of fish; digestive cell atrophy in the oyster Ostrea edulis; and induction of imposex in the snail Hexaplex trunculus. The latter two responses are evident at TBT concentrations below the environmental quality standard (20 ng TBT l(-1)). The ecological implications of these results are discussed and it is concluded that exposure of marine organisms to TBT in local harbours may be expected to lead to a reduction in the long-term survival of a number of such organisms. For these reasons, both the use of TBT-based antifouling paints for pleasure boats as well as drydock practices need to be controlled by appropriate regulations and their enforcement.     

Analysis and occurrence of estrogenic hormones and their glucuronides in surface water and waste water in The Netherlands

An analytical procedure was developed that enables routine analysis of four estrogenic hormones in concentrations below 1 ng/l in surface water and waste water. The recovery was 88-98% with a limit of detection of 0.1-2.4 ng/l depending on the compound and the matrix measured. This method was used to determine the occurrence of 17 beta-estradiol, 17 alpha-estradiol, estrone and 17 alpha-ethinylestradiol in the aquatic environment in The Netherlands. The data show that estrogenic hormones can be detected at low concentrations (up to 6 ng/l) at some locations in surface water. In selected effluents of waste water treatment plants estrone and 17 beta-estradiol were detected in concentrations in the ng/l range. Concentrations of 17 alpha-estradiol and the contraceptive 17 alpha-ethinylestradiol were in most of these samples below the limit of detection. Hormone glucuronides were not detected in most surface water and effluents.     

Monitoring of trifluoroacetic acid concentration in environmental waters in China

It is critically important and extremely meaningful to determine the concentration of TFA in the environmental water in China. This will create background reference for the effects of analyzing the extensive employment of the substitutes to CFCs in China. In this paper a set of analytical methods was described for use in monitoring of trifluoroacetic acid (TFA) concentration of environmental waters including collecting, pre-treatment measures, preserving, concentrating and derivatization of samples from different kinds of environmental waters. The GC with electrical capture detector (ECD) and headspace auto sampler were used in the analysis. The lowest detection limit of the instrument is 0.0004 ng methyl trifluoroacetic acid (MTFA), and the lowest detected concentration with the method is 3.0 ng/ml TFA. TFA collected in various environmental water samples (including rainfall, inland surface water, ground water, and waste water) from nine provinces and autonomous regions in China have been determined by applying the analytical methods created and defined in this work. The results indicate that the concentrations of TFA in nine rainfalls and three snowfalls through the period from 2000 to 2001 ranged from 25 to 220 ng/l, the TFA concentration in the inland surface water samples ranged from 4.7 to 221 ng/l, the concentration of TFA in groundwater samples collected in Beijing was 10 ng/l, and the TFA concentration in coastal water samples ranged from 4.2 to 190.1 ng/l.     

Levels of DDT and hexachlorocyclohexane in burbot (Lota lota l.) from Russian Arctic rivers

The concentrations of organochlorine pesticides (OCPs =p,p'DDT, p,p'DDD, p,p'DDE, alpha-HCH and gamma-HCH) were measured in the sediments, water and burbot (whole liver and liver lipids) of eight Russian Arctic rivers near their outflows to the Arctic Ocean between 1988 and 1994. DDT was not detected in any river sediments above the limit of quantification (LOQ) of 2.5 ng g(-1) dry wt. Concentrations of DDD and DDE were only found in three of the river sediments above the LOQ of 0.75 ng g(-1) dry wt. DDT and DDE were present in only North Dvina and Pechora river water above the LOQ of 5 ng l(-1), while DDD was not found in any river above this limit. Both alpha- and gamma-HCH were found in all river sediments except for the Kolyma River at concentrations up to 2.4 and 3.5 ng g(-1) dry wt., respectively. In river water, alpha-HCH was as high as 8.6 ng l(-1) in the Ob River and gamma-HCH as high as 7.6 ng l(-1) in the Pechora River. The concentration of both sigmaDDT and sigmaHCH decreased to LOQ levels by about 1992 in both water and sediments. sigmaDDT (up to 70 ng g(-1) wet wt.) and sigmaHCH (maximum 18 ng g(-1) wet wt.) in burbot livers followed a similar temporal trend as in water and sediments. There is a scarcity of OCP data for Russia, but from what is available, we conclude that: (1) contamination of Russian rivers and burbot by OCPs is less severe in the Arctic than at lower latitudes; (2) contamination of Russian Arctic burbot is comparable to, or lower than, similar OCP contamination measured in burbot and other fish in other countries; and (3) the OCP concentrations in Russian burbot pose a negligible health risk to either humans or wildlife.     

小体积直接进样气相色谱法应急监测水中甲醇

建立了水中甲醇的应急监测新方法，采用小体积直接进样、大口径毛细管柱分离、氢火焰离子化检测器气相色谱法，在几分钟内完成了对水中甲醇的快速测定。该方法的线性测定浓度范围为5～500mtg／L，相对标准偏差为l.6％～4.3％，平均加标回收率为88％～93％，标准曲线的相关系数为0．9992，最低检测浓度为0．3mtg／L。测定结果不受其他干扰物质的影响，可用于水中甲醇的应急监测。     

超高效液相色谱-高分辨质谱法测定水体中青霉素残留

采用超高效液相色谱-高分辨质谱法(UPLC-HRMS)同时测定水体中7种青霉素残留。水样经Oasis HLB固相萃取小柱富集和净化后,用反向C18色谱柱分离,以0.1%的甲酸水溶液和乙腈溶液为流动相进行梯度洗脱,采用电喷雾离子源正离子模式进行检测。7种青霉素类化合物在1.0~20.0μg/L的线性范围内,相关系数r均大于0.99,检出限为1~10 ng/L。实际水样加标回收率为91.15%~106.36%,相对标准偏差为2.30%~8.47%,均小于10%。该方法具有简单快速、准确度高等特点,可以实现水体中7种目标青霉素残留的测定。     

TBT in marine sediments and blue mussels (Mytilus edulis) from central-west Greenland

Concentrations of butyltin compounds were investigated in the bivalve Mytilus edulis (five sites) and marine sediments (three sites) near the largest town, Nuuk, in Greenland. In seven of the eight samples the extremely toxic compound tributyltin (TBT) was detected. The concentrations of tributyltin and degradation products in the bivalves were close to 1 microgram kg-1 wet weight (ww), calculated as Sn, which is lower than those found in Iceland and the Faeroe Islands. In sediments the concentration of TBT ranged from below the limit of detection of 1 microgram kg-1 to 171 micrograms kg-1 dry weight (dw), calculated as Sn, which is comparable to levels found in Europe.     

Analysing transformation products of herbicide residues in environmental samples

High-performance liquid chromatography (HPLC) methods were developed for the optimised determination of five herbicide residues (dichlorprop, isoproturon, mecoprop, metsulfuron-methyl and 2,4,5-T) and major metabolites. These compounds represent important groups of herbicides and several residues have been found as contaminants in groundwater. The methods make it possible to study these herbicides and several transformation products through simultaneous detection and quantification. Culture media as well as cleaned up extracts from sediment and groundwater can be analysed. Using HPLC with UV detection the general limit of quantification was 1.8 ng injected corresponding to a detection limit of 1-2 micrograms/l when analysing a cleaned up extract from a 20 ml water sample. The method was verified by analysing herbicide residues in groundwater collected from a wetland area. Cleaning up 20 ml groundwater with a residue level of 25 micrograms/l the general recovery was within 58-82%.     

固相萃取/气相色谱/质谱法测定饮用水中毒死蜱

建立了检测饮用水中毒死蜱的固相萃取/气相色谱/质谱法,该方法对毒死蜱的测定下限可达0.000 6 mg/L,远低于国标法的0.002 mg/L。线性范围为0.5～5.0 mg/L,样品平均加标回收率在74.86%～86.14%之间,测定结果的相对标准偏差<5.4%。该方法简单、灵敏度高、准确、重现性好,可用于饮用水中痕量毒死蜱的测定。     

Butyltins in sediments and deposit-feeding bivalves Scrobicularia plana from Arcachon Bay,France

A survey was conducted in Arcachon Bay during the summer of 1993 to determine the concentrations of tributyltin (TBT) and two degradation products in sediments and deposit-feeding bivalves Scrobicularia plana; the recruitment of juvenile clams to one site was also investigated. The three butyltins were detected in all sediment samples; however, the concentrations of TBT (from 7 to 30 ng Sn g⁻¹) were far lower than the literature values shown to have adverse effects on populations of sediment-dwelling bivalves. TBT levels in adult S. plana were similarly reduced (from 28 to 165 ng Sn g⁻¹), and they were consistently lower than the values predicted by the modelled bioavailability of TBT in sediments. On the other hand, recruitment to that particular site was negligible when compared to that recorded in the 1970s; the same applies to the adult density in this and other sites. This decline of the local S. plana populations is discussed in relation to present and past TBT pollution.     

Stirring bar sorptive extraction in the determination of PAHs in drinking waters

The application of a new extraction technique which is known as stir bar sorptive extraction (SBSE), followed by high-performance liquid chromatography with a fluorescence detector, was assessed for determining eight polycyclic aromatic hydrocarbons (PAHs) in water samples. The extraction conditions such as acetonitrile addition; effects of temperature and salt; and finally, extraction and desorption time profiles were studied. Once SBSE was optimized, analytical method parameters such as linearity (r(2)>0.991), precision (<9%), detection (0.5-7.3 ng/L) and quantitation (1.0-22 ng/L) limits were estimated. To correct for the 43-57% absolute recovery depending on the PAH, calibration was done with a line obtained submitting standard-spiked blank tap waters to the complete sample treatment and analysis. Consequently, relative recovery was about 100% because all water samples (those for calibration purposes and those for recovery estimation) were processed in the same way and the absolute recovery remained constant. SBSE method characteristics were checked with the analysis of real drinking waters in the search for PAHs.     

Flow injection determination of p-aminophenol at trace level using inhibited luminol-dimethylsulfoxide-NaOH-EDTA chemiluminescence

A novel flow injection procedure was developed for the determination of p-aminophenol (PAP) based on the inhibition by PAP of the chemiluminescence from luminol-dimethylsulfoxide (DMSO)-NaOH-EDTA system. The method has merits of higher sensitivity, wider linear range, simpler procedure, and a more rapid analyzing speed. It is applicable for the determination of PAP in the range of 2.5 x 10(-10)-5.0 x 10(-8) g mL(-1) with a detection limit of 1.9 x 10(-10) g mL(-1). The relative standard deviation (RSD) for 5.0 x 10(-9) g mL(-1) PAP is 0.78% (n=15). The method has been successfully used to determine PAP in industrial wastewaters and environmental waters. Additionally, the inhibition mechanism was also discussed briefly.     

Polychlorinated biphenyls (PCBs) in sediments of the southern Baltic Sea--trends and fate.

Polychlorinated biphenyls (PCBs) have been determined in recent [0-1(2), 1(2)-5 and 5-10 cm deep layers] sediments from different sites of the southern Baltic Sea, including the Szczecin Lagoon, collected from May 1996 to October 1999, i.e. before and after the great flood in Poland of July/August 1997. The PCB distribution has been correlated with location and hydrological conditions as well as with organic carbon, algal pigments and their derivatives in the sediments. The sum of PCB (seven congeners) was equal to approximately 1-149 ng/g dry wt., on average this was rather low (up to 40 ng/g). There was a decreasing trend in PCBs concentrations in the bottom sediments of the southern Baltic in 1996 but considerable amounts were still accumulated there. The flood of 1997 caused a distinct increase of PCB concentration level in the sediments, which again showed a decreasing trend in the next few years. This illustrates that at present the main source of PCBs for the southern Baltic are not a direct consequence of human activity, but from floods and heavy rains washing these compounds from land to the sea. Algae and algal detritus play an important role in the transport and distribution of PCBs in the southern Baltic. High correlation of PCBs with chlorophyll a derivatives--products of zooplankton grazing--indicates that PCBs are ingested by zooplankton with phytoplankton and then exuded with fecal pellets. PCBs bound to algal detritus or to fecal pellets in the water column are transferred to sediments, there they may be trapped either in a bonded and unchanged form or resuspended, remobilized and/or dechlorinated, depending on their properties and environmental conditions.     

Distribution of silicones in water, sediment and fish in Japanese rivers

A new analytical method for assaying polyorganosiloxanes (silicones) in environmental samples is presented. The method utilizes petroleum for solvent extraction of the sample (water, sediment, biological tissue) together with inductively coupled plasma detection of the extracted organic silicones. The detection limit for silicones in the final methyl isobutyl ketone sample/extract is approximately 0.01 ppm, and the method is applied to samples from various Japanese rivers to quantify silicones in several environmental materials. Silicones are reported from river waters (up to approximately 50 ppb), riverine sediments (up to 6 ppm), and as an extractable component of fish tissue (up to approximately 0.9 ppm).     

Analysis of the antioxidant butylated hydroxytoluene (BHT) in water by means of solid phase extraction combined with GC/MS

The antioxidant 3,5-di-tert-butyl-4-hydroxy-toluene (BHT) is widely used as an additive to increase the tenability of food and plastics. BHT is degraded to 3,5-di-tert-butyl-4-hydroxybenzaldehyde (BHT-CHO) in mammals, as well as in the natural environment such as in water and soils. BHT-CHO has been studied extensively in terms of their potential toxicities. The present investigation was carried out to quantify BHT and BHT-CHO in river, ground, rain and drinking water obtained from several locations in Germany. Apart from the compounds mentioned above, 1,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)ethane (2-BHT), which is a dimer of BHT, was also detected in the extracts of some ground water samples. The applied analytical method is based on solid phase extraction (SPE) to concentrate trace compounds from water samples followed by gas chromatography/mass spectrometry (GC/MS) of the extracts. A total of 51 of the respective water samples were used for extraction purposes and analyte recoveries were all > or = 80%. The determination limit for BHT was 5 ng l(-1) and for BHT-CHO 16 ng l(-1). The standard deviations for the analytical procedure were 6% for BHT and 10% for BHT-CHO. The use of the antioxidant BHT in Germany has resulted in water concentrations of 7-791 ng l(-1) in the rivers Rhine, Elbe, Main, Oder, Nidda and Schwarzbach. The degradation product BHT-CHO was also detected in the river water samples at concentrations between 29 and 223 ng l(-1). The concentrations of BHT measured in German rivers are lower compared to values measured in the USA and Japan 20 years ago. In ground water, levels for BHT varied from non-detectable up to 2156 ng l(-1) and for BHT-CHO from non-detectable up to 674 ng l(-1). Both compounds were also detected in rain water in Frankfurt/Main at a concentration of 1797 ng l(-1) for BHT and 59 ng l(-1) for BHT-CHO.     

Organotin survey in the Adour-Garonne basin

Organotin monitoring was performed in waters of 11 rivers of the southwest of France during a 9 months period, between February and October 2001. Surface sediments were studied during the summer. Eighteen sampling points were chosen as representative of specific industrial or agricultural activities. In most samples, organotins were detected and butyltins are the most frequently present, with concentrations ranging over 0.2-30 ng(Sn)/L. Phenyltins were detected especially in spring and at the end of summer, which corresponds to likely diffusion from agricultural sources. Some high butyl- and phenyltin concentrations up to 700 ng(Sn)/L occurred during the spring where pesticides for agricultural activities were largely used. Octyltins were present in water frequently as well, with lower concentrations, probably originating from continuous leaching of plastics. Sediments appeared contaminated by the same species, with higher monobutyltin concentrations of about 30-40 microg(Sn)/kg which shows the importance of biological degradations occurring in surface sediments. This non-pesticidal organotin compounds can also be introduced from leaching of organotin-stabilized PVC by water. Using the different organotin concentrations obtained and other physico-chemical parameters measured, such as temperature or water flow rate, a statistical study was performed by principal component analysis. The results obtained allow the main sources of organotin diffusion to be identified and the hydrological cycle of these compounds better understand.     

微波消解原子荧光光谱法测定活性污泥中的砷

利用高压密闭微波消解技术消解城市污水处理厂污泥样品,并采用氢化物发生/原子荧光光谱法测定污泥中的砷,设定了最佳的样品处理与仪器测定条件。在0.00～200μg/L之间,标准曲线的线性相关系数达0.999 0以上,以称样0.200 0 g计,检出限为0.005 mg/kg。通过测定国家标准物质和加标回收试验,进行了方法验证,其精密度和准确度均能满足污泥环境样品的测试要求。在试验条件下,测定样品中砷的加标回收率为96%～102%,测定结果的RSD<2%。     

Measurement of volatile organic compounds in sediments of the Scheldt estuary and the Southern North Sea

The concentrations and distribution of 13 priority volatile organic compounds (VOCs) were determined in sediments of the Scheldt estuary and the Belgian continental shelf, using a modified Tekmar LSC 2000 purge-and-trap system coupled to GC-MS. The method allows a sample intake of up to 50 g wet weight and detection limits are between 0.003 ng/g (tetrachloromethane) and 0.16 ng/g (m- and p-xylene). The repeatability (n = 5) varied between 4% (benzene) and 17% (toluene) and the recoveries ranged from 59% (1,1-dichloroethane) to 99% (tetrachloromethane). Because of the nature of the contaminants, special attention was paid to analyte losses and contamination of the samples during storage aboard the research vessel. Spiked sediment samples were prepared in the laboratory and stored aboard under the same conditions as the environmental samples. The recoveries for these samples varied between 94 and 130%, which suggests that storage had no adverse effect on the samples. No detectable VOC concentrations were found for most of the sampling stations. However, in the Antwerp harbour area, significant concentrations of VOCs were found. The sorption behaviour as predicted from laboratory equilibrium partitioning experiments gives an indication of the in situ partitioning behaviour of VOCs. Although VOCs in sediments should, in general, not be regarded as a major problem in the marine environment, high local concentrations may be a cause of concern.     

Determination of Irgarol 1051 in Western Mediterranean sediments. Development and application of supercritical fluid extraction-immunoaffinity chromatography procedure

A supercritical fluid extraction (SFE) procedure for Irgarol 1051 (i.e. 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine) determination in marine sediments, which minimises the solvent usage, is developed and compared to a conventional extraction technique (i.e. sonication). First, the use of methanol (MeOH) in the presence of trifluoroacetic acid (TFA) as secondary modifier of supercritical carbon dioxide was evaluated. Extraction efficiency was strongly dependent on the modifier content but lesser on pressure (100-410 bar) and temperature (60-200 degrees C). In the selected extraction conditions (20% MeOH/TFA 0.65M, 370 bar, 150 degrees C) recoveries higher than 87% were obtained and the limit of detection was 3 ngg(-1) and the relative standard deviation of 10% (N=3) by GC coupled to mass spectrometry (GC-MS) in the electron impact mode. The developed SFE procedure is more convenient to extract Irgarol 1051 than the agitation plus sonication methods concerning on solvent usage (1.5 vs. 20 mL) being compatible with immunochemical procedures avoiding any solvent transfer step. The developed SFE combined with immunoaffinity chromatography (IAC) is highly selective allowing the determination of Irgarol by gas chromatography with nitrogen-phosphorus detection or in sediments at low ngg(-1) level (11-35 ngg(-1)) from Mediterranean marina and harbour sediments.     

微波萃取/HPLC法测定污泥中的烷基酚类物质

采用微波辅助萃彬高效液相色谱法对深圳市龙岗区供水集团有限公司各水厂的沉淀池和回收水池池底污泥中烷基酚类和烷基酚聚氧乙烯醚类化合物的浓度进行了测定，并与采自周围环境中的样品进行了比较，该方法的检测限为0.010～0．050mg／L，回收率为95．47％～106．42％，测定结果的相对标准偏差为0．86％～5．20％。