Determination of pollution trends in an abandoned mining site by application of a multivariate statistical analysis to heavy metals fractionation using SM&T-SES

The mobility, availability and persistence of Heavy Metals (HMs), As, Cd, Cu, Ni, Pb and Zn, in contaminated soils of a former abandoned mining area were evaluated by means of a sequential extraction scheme (SES) and applying a multivariate statistical analysis to the obtained data. Chemical partitioning of HMs in each sample was determined in four fractions (acid-soluble, reducible, oxidable and residual) following the Standard Measurements and Testing (SM&T) SES, formerly BCR-SES. Statistical evaluation of results by pattern recognition techniques allowed identification of groups of samples with similar characteristics and observations of correlations between variables, determining the pollution trends and distribution of HMs within the studied area. Typical metal-fraction association and metal availability characteristics of heavy metals have been depicted. The obtained results indicate an urgent need to attenuate the hazard in that area posed by high concentrations of toxic metals, which exceed the limits specified by different European legislations on soil reclamation.     

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.     

A modular approach to Integrated Assessment modeling

In this paper, we present a new approach to model coupling that probably forms the methodological basis of a new generation of Integrated Assessment models. This approach respects the knowledge and expertise that is embodied in existing models and encourages their gradual evolution. Modularity is the guiding principle. Our approach is distinguished by the way modules are coupled which is based on an interplay of a job control module, a numerical coupling module, and a couple of stand-alone functional modules. The numerical coupling module - the core component - serves to treat the feedbacks between the functional modules. A first implemented example that couples an economic and a climate module by means of a two-phase meta-optimization is presented here. The algorithm and mathematical structure behind are discussed as well as important features such as convergence behavior and reliability.     

Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.     

The Monitoring and Risk Assessment of Zn Deposition Around a Metal Smelter in Latvia

Heavy metal concentrations in Hylocomium splendens collected around a metal smelter in Latvia showed very high concentrations of Zn (>200 g/g), and elevated concentrations of Pb (38.3 g/g) and Cu (18.3 g/g). In an attempt to better evaluate the potential toxicity of the high Zn concentrations, a serial elution method was used to determine the concentrations of zinc in intercellular, extracellular exchangeable cell wall, intracellular, and particle fractions. The intercellular Zn concentrations represent the water soluble component of the total concentrations, and were low with no clear trends. Zn concentrations in the extra- and intracellular and particle fractions decreased exponentially from the pollutant source. Intracellular Zn concentrations in moss close to the emission source are within the range considered to be potentially toxic, from other single element exposure studies. The proportion of Zn in the relatively insoluble particle fraction, which is least associated with environmental risk, was greater closer to the pollution source, reaching > 30% in the oldest Hylocomium splendens segments.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

Water quality test based on dielectrophoretic measurements of fresh water algae Selenastrum capricornutum

A method is described whereby dielectrophoresis of algal cells is used to perform rapid water quality analysis, specifically detecting the presence of CuSO4. The dielectric collection spectrum of the fresh water alga Selenastrum capricornutum was determined for a range of concentrations of CuSO4 from 25 mg L(-1) to 0.25 mg L(-1) for exposure times of 15 min and 18 h. In all cases increasing the concentration of CuSO4 reduced cell collection, but a step reduction was observed in collection between 2 mg L(-1) and 5 mg L(-1). This method has potential for forming a rapid, low-cost test for water quality with broad specificity and significantly reduced analysis time compared to current methods.     

Monitoring of the three organophosphate esters TBP,TCEP and TBEP in river water and ground water (Oder,Germany)

The behaviour of the three organophosphate esters tributyl phosphate (TBP), tris(2-chloroethyl)phosphate (TCEP) and tris(2-butoxyethyl)phosphate (TBEP) during infiltration of river water to ground water has been investigated. The monitoring site is the Oder River and the adjacent Oderbruch aquifer. From March 2000 to July 2001, 76 ground water samples from monitoring wells located close to the Oder River and nine river water samples were collected. Additionally, influent and effluent samples from local waste water treatment plants, one sample of rain water and samples of roof runoff were collected. All samples were analysed by solid-phase-extraction followed by gas chromatography/mass spectrometry. TBP, TCEP and TBEP were detected at mean values of 622 ng l(-1), 352 ng l(-1), and 2955 ng l(-1), respectively in municipal waste water effluents. This points to a major input of these compounds into the Oder River by municipal waste water discharge. The concentrations of TBP and TBEP decreased downstream the Oder River possibly due to aerobic degradation. TBP, TCEP and TBEP were detected in ground water influenced predominantly by bank-filtered water. This demonstrates a transport of organic compounds by river water infiltration to ground water. TBP, TCEP and TBEP were also detected in rain water precipitation, roof runoff and ground water predominantly influenced by rain water infiltration. This hints to an input of these compounds to ground water by dry and wet deposition after atmospheric transport. Organophosphate esters were also detected in parts of the aquifer at 21 m depth. This demonstrates low anaerobic degradation rates of TBP, TCEP and TBEP.     

Optimizing the removal of small fish passage barriers

Removing small artificial barriers that hinder upstream migrations of fish is a major problem in riparian habitat restoration. Because of budgetary limitations, it is necessary to prioritize barrier removal and repair decisions. These have usually been based on scoring and ranking procedures, which, although simple to use, can be very inefficient in terms of increasing the amount of accessible instream habitat. We develop a novel decision-making approach, based on integer programming techniques, which optimizes repair and removal decisions. Results show based on real datasets of barrier culverts located in Washington State that scoring and ranking is over 25% below the optimum on average and a full 100% below in the worst case, producing no net habitat gain whatsoever. This is compared to a dynamic programming method that was able to find optimal solutions in less than a second, even for problems with up to several hundred variables, and a heuristic method, which found solutions with less than a 1% average optimality gap in even less time.