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.     

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.     

Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

Assessment of the Usefulness of Semipermeable Membrane Devices for Long-Term Watershed Monitoring in an Urban Slough System

Semipermeable membrane devices (SPMDs) were deployed at eight sites within the Buffalo Slough, near Portland, Oregon, to (1) measure the spatial and seasonal distribution of dissolved polycyclic aromatic hydrocarbon (PAH) and organochlorine (OC) compounds in the slough, (2) assess the usefulness of SPMDs as a tool for investigating and monitoring hydrophobic compounds throughout the Columbia Slough system, and (3) evaluate the utility of SPMDs as a tool for measuring the long-term effects of watershed improvement activities. Data from the SPMDs revealed clear spatial and seasonal differences in water quality within the slough and indicate that for hydrophobic compounds, this time-integrated passive-sampling technique is a useful tool for long-term watershed monitoring. In addition, the data suggest that a spiking rate of 2–5 μg/SPMD of permeability/performance reference compounds, including at least one compound that is not susceptible to photodegradation, may be optimum for the conditions encountered here.     

Genotoxicity evaluation of water soil leachates by Ames test, comet assay, and preliminary Tradescantia micronucleus assay

Combining genotoxicity/mutagenicity tests and physico-chemical methodologies can be useful for determining the potential genotoxic contaminants in soil samples. The aim of our study was to evaluate the genotoxicity of soil by applying an integrated physico-chemical-biological approach. Soil samples were collected at six sampling points in a Slovenian industrial and agricultural region where contamination by heavy metals and sulphur dioxide (SO₂) are primarily caused by a nearby power plant. The in vitro alkaline version of the comet assay on water soil leachates was performed with Caco-2 and HepG2 cells. A parallel genotoxicity evaluation of the samples was performed by Ames test using Salmonella typhimurium and the Tradescantia micronucleus test. Pedological analyses, heavy metal content determination, and different physico-chemical analyses, were also performed utilizing standard methodology. Water leachates of soil samples were prepared according to standard methods. Since only a battery of biotests with prokaryotic and eukaryotic organisms or cells can accurately estimate the effects of (geno)toxicants in soil samples and water soil leachates, a combination of three bioassays, with cells or organisms belonging to different trophic levels, was used. Genotoxicity of all six water soil leachates was proven by the comet assay on both human cell lines, however no positive results were detected by bacterial assay, Ames test. The Tradescantia micronucleus assay showed increase in micronuclei formation for three samples. According to these results we can assume that the comet assay was the most sensitive assay, followed by the micronucleus test. The Ames test does not appear to be sensitive enough for water soil leachates genotoxicity evaluations where heavy metal contamination is anticipated.     

The Use of Mytilus Galloprovincialis Acetylcholinesterase and Glutathione S-Transferases Activities as Biomarkers of Environmental Contamination Along the Northwest Portuguese Coast

With the aim of using Mytilus galloprovincialis acetylcholinesterase (AChE) and glutathione S-transferases (GST) activities as biomarkers of environmental contamination in risk assessment studies along the northwest Portuguese coast, the objective of this study was to provide background information related to: (1) baseline values of these enzymatic activities both in reference and contaminated areas and their responsiveness as indicators of exposure to environmental contaminants; (2) the importance of seasonal variations of such biomarkers in M. galloprovincialis along this area. For this, the activity of these enzymes was seasonally determined in mussels collected from four sites, including a reference and three stations with different contamination sources along the referred area. Statistically significant differences on both enzymatic activities were found among the four sampling stations, at the four sampling periods. In comparison to the reference station, lower AChE and higher GST activity values were found in mussels collected in stations potentially contaminated by pesticides and domestic/industrial effluents and in mussels collected in the vicinity of an oil refinery and an industrial/mercantile harbour, respectively. The results obtained in this work highlighted the potential suitability of these biomarkers to be used as components of environmental monitoring programs in risk assessment studies along the northwest Portuguese coast. Since a seasonal variation in both enzymatic activities was found, the possible implications of such variability in the use of these enzymes as environmental biomarkers are also discussed.     

Oxidative DNA damage levels and catalase activity in the clam Ruditapes decussatus as pollution biomarkers of Tunisian marine environment

Levels of the oxidative DNA damage 7, 8-dihydro-8-oxo-2′-deoxyguanosine (8-oxodG) and catalase (CAT) activity were measured in the digestive gland and gills of clams Ruditapes decussatus, related to the presence of pollutants along Tunisian marine environment. Increased levels of CAT were observed in tissues of clams from all the sites studied, compared to control values, and elevated 8-oxodG levels were observed at specific sites. Results obtained in this work indicate that the measurement of 8-oxodG levels and CAT activity in tissues of R. decussatus is promising in pollution monitoring studies of the Tunisian marine environment.     

Monitoring bio-available marine contaminants with mussels (Mytilus edulis L) in the Netherlands

After discussing the usefulness of mussels (e.g. Mytilus edulis) for investigating contamination in the marine environment, four cases are presented:

1. A survey of Cu bioavailability in and around the Eastern Scheldt during one winter (1974–1975);
2. A surveillance with a six years interval (1974; 1980) of the bioavailability of Zn along the Dutch North Sea coast.
3. A monitoring programme over the period 1972–1980 showing the decrease in bioavailable Hg in the water column of the Ems-Dollard estuary after decreased emissions at Delfzijl.
4. Retrospective monitoring of two PCB's, as a background for the effectiveness of legal restrictions to PCB use.

These four cases are considered a first step in understanding the effects of pollutants in marine ecosystems. In depth physiological, histological and biochemical studies could lay the basis for improved routine biological effect monitoring.     

A simple method for the extraction of mutagens from airborne particles

Organic materials were extracted with acetone from filters of airborne particles by soaking, shaking, soxhletion, and sonication. These extracts were tested with and without S9 for mutagenicity using Ames assay and arabinose-resistant assay of Salmonella typhimurium. Among the extraction methods, soaking extract had the highest mutagenic activity followed by sonication, shaking, and soxhletion in both the assays. With the samples studied, it was concluded that soaking with acetone for 1/2 hr is the simplest and an efficient procedure for the extraction of mutagens from airborne particles.Results of cooperative investigation of NIOSH and West Virginia Agricultural and Forstry Experimental Station. Published with the approval of the Director of the West Virginia Agricultural and Forestry Experiment Station as Scientific Paper No. 1822.     

Enteromorpha flexuosa (Wulfen) J. Agardh (Chlorophyta: Ulvales)--evaluation as an indicator of heavy metal contamination in a tropical estuary

The use of bioindicators for contaminant monitoring ispopular in all sectors of the environment but quite oftenbioindicators are utilised without rigorous evaluation oftheir viability as an indicator. We report field andlaboratory investigations into the value of a commonlyfound macroalga, Enteromorpha flexuosa (Wulfen) J.Agardh (Chlorophyta: Ulvales) as an indicator of copper,zinc and lead contamination in a tropical estuary inFiji. In the laboratory, metal content of E.flexuosa after 60 days of growth in seawater containingincreasing concentrations of the metals showed almostperfect correlation with metal concentrations in waterfor all three metals, and concentration factors obtainedwere generally higher than values reported for otherspecies of Enteromorpha. Performance in the fieldwas evaluated by a one-year monitoring of metals in E. flexuosa, water and sediments from a contaminatedestuary. Metal concentrations in water were always belowdetection limits and field concentration factors couldnot be determined but the concentration of lead in E. flexuosa showed a high correlation with the leadcontent of sediments. Lack of such correlation forcopper and zinc in the field suggests that otherenvironmental factors besides metal load in the physicalenvironment could be controlling the bioaccumulation ofthese two metals. Whilst demonstrating E. flexuosato be a viable bioindicator for lead, these results alsohighlight the need for proper assessment before anorganism is considered for environmental monitoring.