Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment.

We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.

Nutrient, pigment, suspended matter and turbidity measurements in the Belgian part of the North Sea.

Through regular sampling surveys, the Flanders Marine Institute is generating long term data series for the Belgian coastal water and sand bank systems, a designated site in the Long Term Ecological Research (LTER) network. The data series is built on sampling activities initiated in 2002, but gradually upgraded and extended in the framework of the LifeWatch marine observatory and the Integrated Carbon Observation System (ICOS) participation. Nine nearshore stations are sampled monthly, with additional seasonal sampling of eight offshore stations. This paper presents the generated data series for nutrients, pigments, suspended matter and turbidity. The collection, methodology and processing of the 2002-2018 dataset is described, along with its data curation, integration and quality control. Yearly versions of the data are published online in a standardized format, accompanied with extensive metadata description and labelled with digital identifiers for traceability. Data is published under a CC-BY license, allowing use of the data under the condition of providing reference to the original source.

Realistic environmental mixtures of hydrophobic compounds do not alter growth of a marine diatom.

In this paper we determine whether a realistic mixture of hydrophobic chemicals affects the growth dynamics of a marine diatom and how this effect compares to the effect of temperature, light regime and nutrient conditions. To do so, we examine the specific growth rate of Phaeodactylum tricornutum in a 72 h algal growth inhibition test using a full factorial design with three nutrient regimes, two test temperatures, three light intensities and three chemical exposures. Passive samplers were used to achieve exposure to realistic mixtures of organic chemicals close to ambient concentrations. Nutrient regime, temperature and time interval (24, 48 and 72 h) explained 85% of the observed variability in the experimental data. The variability explained by chemical exposure was about 1%. Overall, ambient concentrations of hydrophobic compounds present in Belgian coastal waters, and for which the passive samplers have affinity, are too low to affect the intrinsic growth rate of P. tricornutum.

n-Alkanes and stable C, N isotopic compositions as identifiers of organic matter sources in Posidonia oceanica meadows of Alexandroupolis Gulf, NE Greece.

We analyzed n-alkane contents and their stable carbon isotope composition, as well as the carbon and nitrogen isotope composition (δ(13)C, δ(15)N) of sediment organic matter and different tissues of Posidonia oceanica seagrass sampled in Alexandroupolis Gulf (A.G.), north-eastern Greece, during 2007-2011. n-Alkane contents in P. oceanica and in sediments showed similar temporal trends, but relative to bulk organic carbon content, n-alkanes were much more enriched in sediments compared to seagrass tissue. Individual n-alkanes in sediments had similar values than seagrass roots and rhizomes and were more depleted in (13)C compared to seagrass leaves and sheaths, with δ(13)C values ranging from -35‰ to -28‰ and from -25‰ to -20‰, respectively. n-Alkane indexes such as the Carbon Preference Index, carbon number maximum, and n-alkane proxy 1 (C23+C25/C23+C25+C29+C31) indicate strong inputs of terrestrial organic matter, while the presence of unresolved complex mixtures suggests potential oil pollution in some sampled areas.

Modelling the fate of micropollutants in the marine environment using passive sampling.

Polydimethylsiloxane sheets were used to determine freely dissolved concentrations (C(diss)) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the Belgian coastal zone. Equilibrium models were used to predict the whole water concentrations (C(ww)) of these compounds as well as their concentrations in sediment, suspended particulate matter (SPM) and biota. In general, contaminant concentrations were predicted well for whole water and biota. C(ww) was increasingly underpredicted as K(oc) increased, possibly because of the presence of black carbon. Concentrations in biota were overestimated by the equilibrium approach when logK(ow) exceeded 6.5, suggesting an increasing role of transformation processes. Concentrations of PAHs and PCBs in sediment and SPM were consistently underpredicted although a good correlation between measured and predicted values was observed. This was potentially due to the use of experimental K(oc) values which have been found to underestimate partitioning of hydrophobic substances to sediment in field studies.

Passive sampling reversed: coupling passive field sampling with passive lab dosing to assess the ecotoxicity of mixtures present in the marine environment.

This study presents a new approach in aquatic toxicity testing combining passive sampling and passive dosing. Polydimethylsiloxane sheets were used to sample contaminant mixtures in the marine environment. These sheets were subsequently transferred to ecotoxicological test medium in which the sampled contaminant mixtures were released through passive dosing. 4 out of 17 of these mixtures caused severe effects in a growth inhibition assay with a marine diatom. These effects could not be explained by the presence of compounds detected in the sampling area and were most likely attributable to unmeasured compounds absorbed to the passive samplers during field deployment. The findings of this study indicate that linking passive sampling in the field to passive dosing in laboratory ecotoxicity tests provides a practical and complimentary approach for assessing the toxicity of hydrophobic contaminant mixtures that mimics realistic environmental exposures. Limitations and opportunities for future improvements are presented.

Evaluation of a high-resolution time-of-flight mass spectrometer for the gas chromatographic determination of selected environmental contaminants.

A benchtop high-resolution time-of-flight mass spectrometer (TOF MS) was evaluated for the determination of key organic microcontaminants. The major advantage of the TOF MS proved to be the high mass resolution of about 0.002 Da (10 ppm). Consequently, the detectability of polar pesticides, polynuclear aromatic hydrocarbons and polychlorinated biphenyls is excellent, and detection limits are in the order of 1-4 pg injected mass. Best mass spectral resolution was obtained for medium-scale peaks. It is a disadvantage that the calibration range is rather limited, viz. to about two orders of magnitude. The high mass spectral resolution was especially useful to improve the selectivity and sensitivity when analyzing target compounds in complex samples and to prevent false-positive identifications.

Estrogenic and toxic effects of methoxychlor on zebrafish (Danio rerio).

Although zebrafish (Danio rerio) have been suggested as a good candidate for screening potential endocrine disruptors, little information is available on the effects of weak estrogens on this species. We investigated the sensitivity of different life stages of zebrafish toward toxic and estrogenic properties of methoxychlor (MXC). Short-term tests with adults resulted in a sex-specific 96-h lethal concentration for 50% (LC50) of the test animals of 36 microg/L for males and 129 microg/L for females. To determine the estrogenic capacity of MXC, adult zebrafish were exposed to 0, 0.5, 5, and 50 microg MXC/L for 14 d. Induction of vitellogenin ([VTG] measured with protein electrophoresis and Western blot) in males was detected at 5 and 50 microg MXC/L. Females, however, did not exhibit higher blood VTG concentrations at the tested MXC concentrations. In a second series of experiments, juvenile zebrafish were exposed to 0, 0.05, 0.5, and 5 microg MXC/L for 33 d. Survival, length, weight, and condition of larvae were examined as indicators of toxic stress and the VTG content in whole body homogenates of juveniles was measured to determine xenoestrogenic effects. No effects of the tested concentrations of MXC were observed. Finally, the effect of MXC on zebrafish eggs, exposed to 0, 1, 10, and 32 microg MXC/L, was examined. Hatching and survival of hatched zebrafish were affected at 10 and 32 microg MXC/L. This study demonstrated that adult male zebrafish are sensitive toward the estrogenic effects of MXC. However, the use of VTG induction to detect effects of (xeno)estrogens in early life stages has to be further investigated, as low concentrations of VTG were detectable in exposed as well as unexposed juvenile fish.

Monitoring polycyclic aromatic hydrocarbons in the Northeast Aegean Sea using Posidonia oceanica seagrass and synthetic passive samplers.

The concentrations of 22 polyaromatic hydrocarbons (PAH) in Posidonia oceanica seagrass, sediments, and seawater from the Alexandroupolis Gulf in the Aegean Sea, were investigated from 2007 to 2011. Temporal trends of total PAH contents in P. oceanica and sediments were similar. PAH levels in seawater, sediments, and seagrasses generally decreased with increasing distance from Alexandroupolis Port. Leaves and sheaths of P. oceanica had higher PAH levels than roots and rhizomes. P. oceanica accumulates PAHs and has good potential as a bioindicator of spatiotemporal pollution trends. PAH concentrations were also examined using in situ passive seawater sampling and were compared to results of passive sampling in the laboratory using local sediments and seawater. Levels of high molecular weight PAHs assessed using passive samplers confirmed the decreasing gradient of pollution away from Alexandroupolis Port. Passive sampling also proved useful for investigating sources of PAHs in P. oceanica meadows.

Additive modelling reveals spatiotemporal PCBs trends in marine sediments.

We developed generalised additive mixed models (GAMMs) to infer spatiotemporal trends of environmental PCB concentrations from an extensive dataset (n=1219) of PCB concentrations measured between 1991 and 2010 in sediments of the Belgian Coastal Zone (BCZ) and the Western Scheldt estuary. A GAMM with time, geographical zone, periodicity and the organic carbon - water partition coefficient as covariates explained 49% of the variability in the log transformed PCB sediment concentrations. The time trends unraveled two to threefold PCB concentration decreases in the BCZ during the last 20 years. However, in the Western Scheldt estuary, time trends were spatially heterogeneous and not significantly decreasing. These results demonstrate that international efforts to cut down emissions of PCBs have been effective to reduce concentrations in open water ecosystems like the BCZ but had little effect in the urbanised and industrialised area of the Scheldt estuary.

Application of a silicone rubber passive sampling technique for monitoring PAHs and PCBs at three Belgian coastal harbours.

A 4-year monitoring was performed to study the freely dissolved water concentrations of PAHs and PCBs in three coastal harbours and at an offshore station in the North Sea. The results are part of a more extensive study to provide information on occurrence, distribution and effects of pollutants in the Belgian coastal zone. Several methods for the estimation of freely dissolved water concentrations are reported in the literature. In the present study silicone rubber passive samplers were used. The non-linear least-square (NLS) method proved to be suitable for estimating sampling rates when using the following performance reference compounds: fluorene-d10, phenanthrene-d10, fluoranthene-d10, benzo(e)pyrene-d12, coronene-d12, CB10, CB14, CB50, CB104, CB145 and CB204. The application of two NLS methods for estimating the sampling rate (Rs) resulted in significant differences for freely dissolved concentrations for individual compounds of up to 30% between the two methods. A model that takes into account the decrease of sampling rate for compounds with higher molecular weight should give a more accurate Rs and was the preferred estimation method. Rs varied from 0.9 to 34.8Ld(-1) for the different target compounds, while estimated freely dissolved concentrations for sum 15 PAHs varied between 3.9 and 170ngL(-1) and for sum 14 PCBs between 0.030 and 3.1ngL(-1). The stations located within marinas showed the highest level of contamination, while the offshore station (5 mile from coastline) exhibited the lowest level. The implications of the use of passive samplers for monitoring programs are discussed.

Monitoring micropollutants in marine waters, can quality standards be met?

The environmental risks of 33 micropollutants occurring in Belgian coastal zone were assessed as single-substances and as mixtures. Water and sediment samples were taken in harbors, coastal waters and the Scheldt estuary during 2007-2009. Measured environmental concentrations were compared to quality standards such as Predicted No Effect Concentrations (PNECs), Environmental Quality Standards (EQSs), and Ecotoxicological Assessment Criteria (EAC). Out of a total of 2547 samples analyzed, 232 and 126 samples exceeded the EQS and EAC, respectively. Highest risks were observed for TBT, PBDEs, PCBs and the PAHs anthracene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, benzo(k)fluoranthene, and benzo(b)fluoranthene in the water compartment and for TBT and PCBs in the sediment compartment. Samples taken at all stations during the April 2008 campaign indicate a potential risk of the contaminant mixtures to the aquatic environment (except W06 station). This study argues the need to revise quality standards when appropriate and hence the overall regulatory implication of these standards.

Polychlorinated biphenyls in marine sediments from the southern North Sea and Scheldt estuary: a ten-year study of concentrations, patterns and trends.

The paper reports the concentrations and patterns of CBs in sediments of the Belgian part of the southern North Sea and the Scheldt estuary for the period 1991-2001. The long-term analytical performance was well within the quality assurance boundaries set at the outset of the study and is consistent with the state of the art for this type of analysis. The CB concentrations (given as the median of the sum of IUPAC Nos 28, 52, 101, 118, 138, 153 and 180) vary between 0.1 microg kg(-1) and 50 microg kg(-1) dry weight in the total sediment and it could be demonstrated that CB patterns in the fine fraction of the sediment were closely similar throughout the investigated area. Isolation of the fine fraction (<63 microm) by sieving can be regarded as a physical normalisation to reduce the differences in sediment granulometric composition. It allows for a better understanding of CB distribution and patterns and improves the trend analysis. A significant downward trend could not be found at any of the stations, which suggests that CB levels have not been changing in the area of interest in the past decade.

Determination of VOCs in yellow eel from various inland water bodies in Flanders (Belgium).

Twenty freshwater eels caught in Flanders (Belgium) were analysed by GC-MS for a total of 52 VOCs. The most prominent VOCs are the BTEX and a number of chlorinated compounds such as chloroform and tetrachloroethene. The observed concentrations which, typically, were in the low ng/g wet weight range, could be linked to the major emission sources and the present study gives new evidence that combustion of fossil fuels is a major source of BTEX in the environment. The concentration levels in eels seem to be a reflection of the actual concentrations in their environment. For eels from the same location similar patterns and concentrations were observed, and the concentrations agree with what can be expected from those of the water column. Generally speaking, the observed concentrations do not seem to pose a threat for organisms. More definite statements will, however, require a larger dataset. The study suggests that the yellow eel can possibly be used as a biomonitor or sentinel organism for VOCs.