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.     

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.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Sampling Benthic Macroinvertebrates in a Large Flood-Plain River: Considerations of Study Design, Sample Size, and Cost

Estimation of benthic macroinvertebrate populations over large spatial scales is difficult due to the high variability in abundance and the cost of sample processing and taxonomic analysis. To determine a cost-effective, statistically powerful sample design, we conducted an exploratory study of the spatial variation of benthic macroinvertebrates in a 37 km reach of the Upper Mississippi River. We sampled benthos at 36 sites within each of two strata, contiguous backwater and channel border. Three standard ponar (525 cm²) grab samples were obtained at each site ('Original Design'). Analysis of variance and sampling cost of strata-wide estimates for abundance of Oligochaeta, Chironomidae, and total invertebrates showed that only one ponar sample per site ('Reduced Design') yielded essentially the same abundance estimates as the Original Design, while reducing the overall cost by 63%. A posteriori statistical power analysis ( = 0.05, = 0.20) on the Reduced Design estimated that at least 18 sites per stratum were needed to detect differences in mean abundance between contiguous backwater and channel border areas for Oligochaeta, Chironomidae, and total invertebrates. Statistical power was nearly identical for the three taxonomic groups. The abundances of several taxa of concern (e.g., Hexagenia mayflies and Musculium fingernail clams) were too spatially variable to estimate power with our method. Resampling simulations indicated that to achieve adequate sampling precision for Oligochaeta, at least 36 sample sites per stratum would be required, whereas a sampling precision of 0.2 would not be attained with any sample size for Hexagenia in channel border areas, or Chironomidae and Musculium in both strata given the variance structure of the original samples. Community-wide diversity indices (Brillouin and 1-Simpsons) increased as sample area per site increased. The backwater area had higher diversity than the channel border area. The number of sampling sites required to sample benthic macroinvertebrates during our sampling period depended on the study objective and ranged from 18 to more than 40 sites per stratum. No single sampling regime would efficiently and adequately sample all components of the macroinvertebrate community.     

Sediment quality in the Douro river estuary based on trace metal contents, macrobenthic community and elutriate sediment toxicity test (ESTT)

The aim of this study was to evaluate the sediment quality in the mesotidal Douro River estuarine environment, in order to identify areas where sediment contamination could cause ecosystem degradation. Samples were obtained in five locations and sediment characterised for grain size, total organic matter, total-recoverable metals (Al, Fe, Cu, Pb, Cr, Ni, Cd, Zn and Mn), as well as acid volatile sulfide (AVS) and simultaneously extracted metals (SEM). In situ effects were evaluated by examining the macrobenthic community structure. An elutriate sediment toxicity test (ESTT) was used to estimate the amount of metals and nutrients that could be exchanged with the water column through resuspension, and its positive or negative effects on the growth of the micro-alga Emiliania huxleyi in a 10 day test. Anthropogenic metal contamination was identified at the north bank of the Douro estuary, with deleterious effects on the macrobenthic community, namely decrease in number of species and diversity. This contamination could possibly also be toxic for water column organisms, in case of resuspension, as shown by the ESTT. Sediments from the salt marsh at the south bank showed an impoverished macrobenthic community and elutriate toxicity, which appeared to be due to anaerobic conditions. This study clearly shows the usefulness of the ESST approach to assess the biological effect of resuspension of estuarine sediments.     

Spatial properties of nutrient concentrations in the Baltic Sea

Using existing monitoring data, the present study attempts to characterize spatial patterns of surface water nutrients in the Baltic Sea. The analysis was made for two different spatial scales, differences between and within sub-basins.Non-parametric methods were chosen to reduce problems with the distributional properties of the data. By dividing the data into four seasons care was taken as to seasonality. To avoid bias due to different laboratory analysis, only data from Nordic countries were used, whose results did not apparently depart from each other. Bias due to different sampling frequency was another problem. This was reduced by using only the last observation in each season for every station and year.The results suggested differences in the nutrient concentrations between basins. The two northernmost basins (Bothnian Bay and Bothnian Sea) had lower phosphate concentrations and higher silicate concentrations compared to the rest of the Sea. Bothnian Bay and the Gulf of Finland had higher nitrate concentrations.The concentration structure within basins was studied using transects in both latitudinal and longitudinal direction. A gradient for phosphate and nitrate was found in the Gulf of Finland, with lower concentrations at the mouth. The Bothnian Sea showed lower concentrations in the middle of the basin compared to the coasts. The highest concentrations of phosphate were found close to the Finnish coast and for silicate the highest concentrations were located near the Swedish coast. It was not possible to study variation in the west-east direction within the Baltic proper, due to data shortage. For the transects in the north-south direction no differences were detected for nitrate and silicate. Phosphate gave one significant result during autumn for the transect in the eastern part of the Baltic proper.This study revealed several problems associated with the data available. Uneven sampling in space and time put severe constraints on the study. A better design of the monitoring program is suggested, where spatial properties are considered explicitly. Revision of the program in this direction is needed for reasonable calculation of total amounts and concentrations representative for a basin.     

Trisomy 7 in chorionic villi: Follow-up studies of pregnancy,normal child,and placental clonal anomalies

Cytogenetic study of chorionic villi sampled because of advanced maternal age revealed, after overnight culture, an apparently non-mosaic trisomy 7. Amniocentesis showed exclusively normal mitoses, and the pregnancy continued normally. One hundred mitoses from cord blood of the normal newborn revealed a non-mosaic 46,XX complement. No cells with a proven trisomy 7 were found in cultures from either of two biopsies of the morphologically normal placenta, but the peripheral biopsy showed in multiple cultures an abnormal clone: 47,XX, + 20,-2,-21, + t(2;21)(p13;q22). To our knowledge, this is the first case of non-mosaic trisomy 7 detected on CVS which has had follow-up studies of amniotic fluid, cord blood, and term placenta.     

Attitudes of women of childbearing age towards prenatal diagnosis in Southeastern France

The objective of this study was to explore women's attitudes towards prenatal diagnosis of trisomy 21 and to examine some of the factors possibly responsible for these attitudes before implementing in real practice serological screening of pregnant women at risk for trisomy 21. We carried out a telephone survey on a representative sample of women who had recently had a normal livebirth delivery in the Marseille district in 1990. The participation rate was 80 per cent and the average age of the mothers was 28-9 years. Among the 514 women interviewed, 78 per cent stated that they would ask for an amniocentesis for a 1 per cent risk of trisomy 21 at their next pregnancy. When adjusting for confounding factors, the decision to have or not to have an amniocentesis was found to depend not only on the women's attitude towards induced abortion, but also on their understanding of the risk involved and on the social context (knowing a handicapped child, discussion with the father). It also depended on the women's age and on what they knew about amniocentesis from the medical point of view. The risk of miscarriage can influence a woman's choice but this objection was not found to affect the women's decisions significantly in our survey. The data showed the existence of a high potential demand for fetal karyotyping.