A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

The influence of geometry and draught shields on the performance of passive samplers

Passive samplers provide an excellent opportunity to perform indicative measurements or establish a dense network of measuring sites. A drawback compared with conventional active measuring methods is the larger spread of results. This variation can, to a large extent, be attributed to the influence of temperature, sampler geometry and wind on sampling results. A proper design of sampler geometry and optimum choice of draught shield can reduce the influence of wind velocity on a badge type sampler to less than 10%. Wire mesh screens prove to be inadequate in damping turbulence. Filters give good results. Attention should be paid to the size and isolation value of the walls of the sampler to prevent thermal updrafts occurring within the sampler. Tube type samplers are less influenced by wind, provided that turbulence is prevented from influencing diffusion within the sampler.     

Exposure and inhalation risk assessment in an aluminium cast-house

To date the exposure, absorption and respiratory health effects of cast-house workers have not been described since most studies performed in the aluminium industry are focused on exposure and health effects of potroom personnel. In the present study, we assessed the external exposure and the absorbed dose of metals in personnel from the aluminium cast house. This was combined with an evaluation of respiratory complaints and the lung function of the personnel. 30 workers from an aluminium casting plant participated and 17 individuals of the packaging and distribution departments were selected as controls. The exposure was assessed by the quantification of total inhalable fume with metal fraction and by the determination of urinary aluminium, chromium, beryllium, manganese and lead concentration. Carbon monoxide (CO), carbon dioxide (CO2), aldehydes and polyaromatic hydrocarbons and man-made mineral fibres concentration were assessed as well. In order to evaluate their respiratory status each participant filled out a questionnaire and their lung function was tested by forced spirometry. Total inhalable fume exposure was maximum 4.37 mg m(-3). Exposure to the combustion gases, man-made mineral fibres and metal fume was well below the exposure limits. Beryllium could not be detected in the urine. The values of aluminium, manganese and lead in the urine were all under the respective reference value. One individual had a urinary chromium excretion above the ACGIH defined biological exposure index (BEI) of 30 microg g(-1) creatinine. There was no significant difference in any of the categories of the respiratory questionnaire and in the results of the spirometry between cast house personnel and referents (Chi-square, all p > 0.05). Exposure in cast houses seem to be acceptable under these conditions. However, peak exposure to fumes cannot be excluded and the potential risk of chromium and beryllium exposure due to the recycling of aluminium requires further attention.     

Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s

Ni and V have been determined in snow and ice collected at a high altitude location (Col du D?me) near the summit of Mont Blanc on the French-Italian border; dated from the 1960s and 1990s. Ni and V were simultaneously determined by inductively coupled plasma sector field mass spectrometry. Measured concentrations range from 6 to 700 pg g(-1) and 4 to 1,100 pg g(-1) for Ni and V, respectively. The results show pronounced seasonal variations in the concentrations of both metals, with high concentration values in summer layers and much lower values for winter layers. These seasonal variations are linked especially with the existence of inversion layers during winter months. Ni and V concentrations in excess of the contributions from rock and soil dust (Ni(excess), V(excess)) appear to be mainly associated with anthropogenic inputs, with pronounced seasonal variations. Large variations in the V(excess)/Ni(excess) ratio are observed, with a higher ratio in summer than in winter. This shows differences in anthropogenic inputs at Col du D?me during the different parts of the year. The above ratio was compared with the corresponding ratios for oil combustion from stationary sources and the exhaust from gasoline and diesel engines. It appears that Ni and V concentrations at Col du D?me are probably the result of changing combinations of contributions from oil combustion for power generation, industrial and residential uses, on one side, and automobile and truck traffic, on the other side, with possibly a significant contribution from Ni smelters in Russia during winter months.     

Identification of dredged sediment-derived soils in the alluvial plains of the Leie and the Upper and Sea Scheldt rivers (Belgium) based on physico-chemical soil properties

An approach was developed to identify surface soils affected by historical dredged sediment disposal in the alluvial plains of the Upper Scheldt, the Sea Scheldt and the Leie river. Dredged sediment-derived soils were identified based on field observations, comparative granulometric analyses and chemical analyses. Criteria developed were based on a comparison between reference data from 102 aerobic soil samples of areas known to be affected by dredged sediment disposal and 104 samples from undisturbed alluvial soils along the studied rivers. A comparative grain size analysis with optical laser diffractometry between the A and C horizon proved useful for the identification of levelled-up sites. The chemical soil characteristics that were most useful in identifying dredged sediment-derived soils were CaCO3, sulfur (S), organic carbon (OC) and phosphorus (P) contents, electrical conductivity (EC), and the C/P and C/S ratios. Criteria for concluding the origin of an investigated soil were specific for the studied area, but the approach presented may provide useful guidelines for developing criteria valid for different regions.     

Field scale variability of cadmium and zinc in soil and barley

CaCl₂-extractable soil Cd and Zn contents have been suggested as a measure of bioavailability. To investigate the ability of this measure to reflect spatial patterns of Cd and Zn concentrations in barley (Hordeum vulgare L.) in an arable field, plant and soil samples were taken from a 0.5 ha area sandy soil contaminated with Cd and Zn. Cd and Zn contents in barley and yield were spatially variable. Yield was low, which may have been caused by Zn toxicity or atrazine turnover. For Cd, CaCl₂-extractable soil contents explained only 17% of the variation in Cd contents in grain, and for Zn no significant correlation was observed. Nevertheless, surface plots of CaCl₂-extractable soil contents and contents of barley grain illustrated their corresponding spatial patterns. Despite the poor linear correlation between CaCl₂-extractable soil-Cd and grain-Cd, a stochastic model for long term behaviour of Cd in field soils predicted observed variability in Cd contents of barley grain well from spatial variability of soil pH and organic matter content. The probabilistic model predicted behaviour of Cd in terms of probability, and was more appropriate than the deterministic approach.     

Application of a checklist for quality assistance in environmental modelling to an energy model

Large, complex energy models present considerable challenges to develop and test. Uncertainty assessments of such models provide only partial guidance on the quality of the results. We have developed a model quality assistance checklist to aid in this purpose. The model checklist provides diagnostic output in the form of a set of pitfalls for the model application. The checklist is applied here to an energy model for the problem of assessing energy use and greenhouse gas emissions. Use of the checklist suggests that results on this issue are contingent on a number of assumptions that are highly value-laden. When these assumptions are held fixed, the model is deemed capable of producing moderately robust results of relevance to climate policy over the longer term. Checklist responses also indicate that a number of details critical to policy choices or outcomes on this issue are not captured in the model, and model results should therefore be supplemented with alternative analyses.     

Determining Ecoregions for Environmental and GMO Monitoring Networks

A representative environmental monitoring network at the regional scale cannot use raster-based or random sampling designs, but requires a stratified sampling procedure integrating different information layers, and it has to occur in ecologically differing homogeneous regions (ecoregions). These we have determined using a set of spatial strata with ecological variables which we analysed with classification and regression trees (CART). We present a framework for environmental monitoring, that covers different scales, and we transfer the framework to a potential GMO (genetically modified organisms) monitoring network. We use ecoregion and other environmental strata together with existing environmental monitoring networks to determine GMO monitoring sites more precisely.     

Monochlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on monochlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programmes in large rivers and estuaries in the North Sea area were collected and evaluated for effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 27 data for fish, 24 data for invertebrates and 13 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 32 micro/l. Recent monitoring data indicate that monochlorobenzene levels in surface waters are below determination limits of 0.1, 0.2, 0.5 microg/l used in monitoring programs. Assuming that half of the lowest determination (0.1 microg/l) is typical, a PEC of 0.05 microg/l was derived. A worst case of 0.5 microg/l is assumed. PEC/PNEC ratios give safety factors of 60 to over 500, taking no account of dilution in the sea. Monochlorobenzene is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Conventions for the Prevention of Marine Pollution (OSPAR-DYNAMEC) criteria. Environmental fate and effects data indicate that current use of monochlorobenzene poses no unacceptable risk to the aquatic environment.