Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.     

Detecting and correcting sensor drifts in long-term weather data

Quality control of long-term monitoring data of thousands and millions of individual records as present in meteorological data is cumbersome. In such data series, sensor drifts, stalled values, and scale shifts may occur and potentially result in flawed conclusions if not noticed and handled properly. However, there is no established standard procedure to perform quality control of high-frequency meteorological data. In this paper, we outline a procedure to remove sensor drift in high-frequency data series using the example of 15-year-long sets of hourly relative humidity (RH) data from 28 stations subdivided into 202 individual sensor operation periods. The procedure involves basic quality control, relative homogeneity testing, and drift removal. Significant sensor drifts were observed in 40.6 % of all sensor operation periods. The drifts varied between data series and depended in a complex, usually inconsistent way on absolute RH values; within single series for instance, a drift could be negative in the lower RH range and positive in the upper RH range. Detrending changed RH values by, on average, 1.96 %. For one fifth of the detrended data, adjustments were 2.75 % and more of the measured value, and in one tenth 4.75 % and more. Overall, drifts were strongest for RH values close to 100 %. The detrending procedure proved to effectively remove sensor drifts. The principles of the procedure also apply to other meteorological parameters and more generally to any time series of data for which comparable reference data are available.     

Ecological quality boundary-setting procedures: the Gulf of Riga case study

Two approaches for setting ecological class boundaries, response curves and a simplified mathematical boundary-setting protocol, were tested for coastal, transitional and open waters in the Gulf of Riga, Baltic Sea. The simplified mathematical boundary-setting protocol defines acceptable ecological status based on expert judgment by a uniform relative deviation from reference conditions. In contrast, response curves derive class boundary definitions from observed changes in biological quality elements along environmental pressure gradients for class boundary definitions. Identification of relevant environmental pressures for the construction of response curves was based on a conceptual model of eutrophication in the Gulf of Riga. Response curves were successfully established for summer chlorophyll a and transparency, as well as for macrozoobenthos abundance in the Central Gulf, macrozoobenthos biotic coefficient in the Southern Gulf, and maximum depth of phytobenthos in the Northern Gulf. In the Gulf of Riga response curves almost always permitted a larger deviation from reference conditions than the 50% deviation applied for the simplified mathematical boundary-setting protocol. The case study clearly demonstrated that class boundary definitions should take into account the sensitivity of the target water body. Also, the class boundaries for different ecological quality elements were internally more consistent than those derived by the simplified mathematical boundary-setting protocol.     

Characterisation of human exposure pathways to perfluorinated compounds--comparing exposure estimates with biomarkers of exposure

Commercially used per- and polyfluorinated compounds (PFCs) have been widely detected in humans, but the sources of human exposure are not fully characterized. The objectives of this study were to assess the relative importance of different exposure pathways of PFCs in a group of Norwegians and compare estimated intakes with internal doses obtained through biomonitoring. Individual PFC intakes from multiple exposure sources for a study group of 41 Norwegian women were estimated using measured PFC concentrations in indoor air and house dust as well as information from food frequency questionnaires and PFC concentrations in Norwegian food. Food was generally the major exposure source, representing 67-84% of the median total intake for PFOA and 88-99% for PFOS using different dust ingestion rates and biotransformation factors of 'precursor' compounds. However, on an individual basis, the indoor environment accounted for up to around 50% of the total intake for several women. Significant positive associations between concentrations of PFCs in house dust and the corresponding serum concentrations underline the importance of indoor environment as an exposure pathway for PFCs. For breast-fed infants, breast milk was calculated to be the single most important source to PFCs by far. The estimated intakes were confirmed by comparing serum concentrations of PFOA and PFOS calculated using PK models, with the corresponding concentrations measured in serum. Even though food in general is the major source of exposure for PFCs, the indoor environment may be an important contributor to human exposure. This study provides valuable knowledge for risk assessment of PFCs and control strategies.     

Empirical relationship between precision and ultra-trace concentrations of PCDD/Fs and dioxin-like PCBs in biological matrices

Dioxin analysis in food and feed can be characterized as an analytical application where very high accuracy is required at very low levels of contamination. Gas chromatography (GC) in combination with 13C-label isotope dilution (ID) high resolution mass spectrometry (HRMS) is the reference congener-specific technique characterized by pronounced selectivity, precision and trueness at parts-per-trillion (ppt) and sub-parts-per-trillion (sub-ppt) levels. The quality of the analytical data produced routinely by a laboratory should be adequate for its intended purpose, i.e., one will seek a compromise between the cost and time needed and the consequences of incorrect decisions due to erroneous results. The requirements for reproducibility are usually dependent on the analyte concentrations and have been expressed in various empirical functions. While Horwitz or modified functions are widely useful for many purposes, it would be difficult to expect these functions to cover every analytical problem. This study reports on precision characteristics achieved by the GC-ID-HRMS reference method for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in food and feed in two interlaboratory method-performance studies among expert laboratories with long-standing experience in this field. Striking linear functions in log scale between reproducibility standard deviation and congener's level over a concentration range of 10(-8)-10(-14)g per g fresh weight are observed. The data fit very well to a Horwitz-type function of the form sR=0.153c0.904, where sR and c are dimensionless mass ratios expressed in pg g(-1) on fresh weight, regardless of the nature of the toxic congeners, food and feed matrices, or sample preparation methods. We demonstrate that the proposed function is suitable for use as a fitness-for-purpose criterion for proficiency assessment in interlaboratory comparisons on dioxins and related compounds in food.     

Integral assessment of estrogenic potentials of sediment-associated samples

GOAL, SCOPE AND BACKGROUND: Exogenic endocrine-active substances are also called 'Endocrine Disrupting Chemicals' (EDC). They imitate or hinder the function of natural endogenic hormones or disturb the synthesis or the metabolism of hormones or of hormone receptors. The Enzyme-Linked Receptor Assay (ELRA) can detect estrogenic and anti-estrogenic effects at the level of receptor binding and is a useful tool for the integrative detection of contaminant effects. Although the test system has been used repeatedly in sediment assessments, the questions have remained concerning how it responds to variations in the physico-chemical matrix. For some bioassays, the salinity of the sample is a critical factor. This is especially relevant when testing wastewater samples or when sediment-associated samples in the tidal reaches of rivers are tested. Sediments in the tidal reaches of rivers change their salinity several times a day. Against this background, it would be beneficial to have a test procedure of known salinity tolerance. On account of this, the salinity tolerance of the ELRA was tested, assessed with reference substances at several salinity levels, and compared with the E-Screen method and a Yeast Estrogen Screen (YES), which are also frequently applied in environmental testing. The aim of this paper was to explore when the salinity limits within these test procedures are applicable. The trials should reveal the working range to be expected, characterize the salinity-dependent variations in sensitivity of the test, and provide options for methodological adjustments to improve the stability against increased salinity. METHODS: The ELRA was carried out with the human Estrogen Receptor alpha. (ER) using the same principle like a competitive immunoassay based on ligand-protein interaction. However, an essential difference is the use of a physiologically relevant receptor instead of an antibody as a linking protein. The ELRA measures the competition of sample estrogens and anti-estrogens against estradiol supplied as a BSA-coating conjugate for the binding site of dissolved ER. Estradiol or xeno-estrogen binding is quantified by a biotynilated anti-ER antibody and the subsequent measurement of peroxidase activity by a streptavidin-POD-biotin complex. The E-Screen was performed with the human breast cancer cell line MCF-7, which expresses the estrogen receptor constitutively. Cell proliferation depends on binding of estrogens or xeno-estrogens with the receptor. After incubation, estrogen-dependent cell growth was measured by sulforhodamin B staining. The YES was performed with a recombinant yeast strain, transfected with a receptor and a reporter plasmid bearing the estrogen receptor and a vitellogenin gene fused with the reporter gene lacZ. Estrogen or xeno-estrogen-dependent gene induction was measured indirectly by LacZ activity. The salinity levels were simulated in varying concentrations with NaCl from 0 to 40 per thousand or Artificial Sea Water (ASW) from 0 to 32 per thousand. RESULTS: The study characterized the factor 'salinity' for the prospective application fields of the ELRA. With reference substances such as 17-beta-estradiol, the ELRA showed classical sigmoidal concentration-effect relations in a range from 0.05 to 100 microg/l under physiological conditions. After a methodological adjustment to compensate decreasing receptor-binding affinity of estrogens and xeno-estrogens at higher salinity levels, the ELRA became applicable under salinity conditions up to concentrations of 20.5 per thousand. In tests, the ELRA reached under the influence of salinity a mean limit of detection of 0.062 microg/l 17-beta-estradiol. The mean relative inter-test error was around 11%. Above concentrations of 20.5 per thousand there is a risk of false negative assessment. Compared with the E-Screen method using the MCF7 cell line and the yeast estrogen test system (YES), the ELRA shows a lower sensitivity to 17-beta-estradiol. In the E-Screen, the cell proliferation was strongly reduced by sodium chloride induced cytotoxicity. In comparison with the E-Screen, the salinity tolerance of the YES and YAS methods is significantly higher. DISCUSSION: Despite adaption, total salinity tolerance could not be achieved with the ELRA. Freshwater samples were generally appraisable. Higher salinity levels above 20.5 per thousand would tend towards false negative results. The low inter-test error of 11% makes the ELRA suitable for the detection of estrogenic and anti-estrogenic potentials of single substances, substance mixtures, and of environmental samples. CONCLUSIONS: The ELRA is very fast and reproducible, it can be used for high-throughput screening in a microplate format at low cost, it is robust to microbial contamination, and is less susceptible to cytotoxic interferences than cell culture methods. RECOMMENDATIONS AND PERSPECTIVES: In their established form, the YES and the E-Screen methods are not applicable for liquid phase testing at higher salinity conditions. The salinity-adapted test version of the ELRA described here shows a broader working range for samples. Native water samples of more or less brackish origin or high-salinity effluent samples are testable. Results of tests with sediment associated samples of different salinity will be subject of a forthcoming publication.     

Reduced analytical availability of polychlorinated biphenyls (PCB's) in colored surface water

It has been generally accepted, during the last few decades, that the dissolved natural organic matter in water [DNOM] appearing as yellow brownish color, has become more and more "polluted" by inorganic and organic micro-pollutants. Due to the complexing properties of NOM, lipophilic organic micro-pollutants, such as, PCBs will be mobilized into water together with the DNOM. A mixture of eight PCBs, with Cl-content from tri-Cl to hepta-Cl, was added to solutions of ten different DNOMs. The DNOMs were aqua's solutions of RO-(reverse osmosis)-isolated material, having approximately the same concentration of carbon. After a contact time of three days, standard analytical PCB-method was used to determine the recovery of the added PCBs. The results show that the analytical availability of the added PCB was significantly reduced in the presence DNOM, compared to distilled water. The percentage loss in recovery of PCB increased with the content of Cl, in mean, from 3%/mg C for tri-Cl to 9%/mg C for hepta-Cl. The results also suggest that the analytical recovery of PCB was affected by the quality and the nature of the organic matter. For example the longer the DNOMs had been in the aquatic phase, the less efficient they are attached to the PCBs.     

Sovereign financial disaster risk management: The case of Mexico

In 2006, Mexico became the first transition country to transfer part of its public-sector natural catastrophe risk to the international reinsurance and capital markets. The Mexican case is of considerable interest to highly exposed transition and developing countries, many of which are considering similar transactions. Risk financing instruments can assure governments of sufficient post-disaster capital to provide emergency response, disaster relief to the affected population and repair public infrastructure. The costs of financial instruments, however, can greatly exceed expected losses, and for this reason it is important to closely examine their benefits and alternatives. This paper analyzes the Mexican case from the perspective of the risk cedent (the Ministry of Finance and Public Credit), which was informed by analyses provided by the International Institute for Applied Systems Analysis (IIASA). The rationale for a government to insure its contingent liabilities is presented along with the fiscal, legal and institutional context of the Mexican transaction. Using publicly available data, the paper scrutinizes the choice the authorities faced between two different risk-transfer instruments: reinsurance and a catastrophe bond. Making use of IIASA's catastrophe simulation model (CATSIM), this financial risk management decision is analyzed within the context of a public investment decision.