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.     

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry

Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

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.     

The efficacy of a limestone doser to mitigate stream acidification in a Maryland coastal plain stream: Implications for migratory fish species

The objective of this two-year study was to determine the efficacy of an automated limestone slurry doser to neutralize acidic pulses and improve water quality conditions for enhancing survival of early life stages of migratory fish species in a Maryland coastal plain stream. Implications for survival of early life stages of migratory fish species such as yellow perch (Perca flavescens), white perch (Morone americana), blueback herring (Alosa aestivalis) and alewife (Alosa pseudoharengus) are discussed based on the improved chemical conditions in the dosed area of the stream. Despite problems with overdosing in 1991 and failure of the stage transducer to work properly in 1992, the doser was generally effective in neutralizing acidic pulses (pH depressions) in the stream during three major rain events in both years. Chemical conditions (pH and inorganic monomeric aluminum) reported in the non-dosed area during major rainfall events were potentially stressful to both alewife and blueback herring although neither species was reported spawning in the stream during either year. Mitigating the potential impact of acidic conditions on early life stages of important migratory fish species was not sufficient to ensure spawning. It is therefore recommended that habitat improvement measures and well designed fish stocking programs be implemented concurrently with doser operations if the goal is to create optimum spawning conditions for migratory species.     

Application of multimedia exposure assessment to drinking water

A potentially important exposure route for humans is the ingestion of chemicals via drinking water. If comprehensive exposure assessments are to be completed for either existing or proposed new chemicals and cost effective control strategies developed, then a quantitative understanding of multimedia transport and fate of specific chemical pollutants must be achieved. Mathematical models provide a powerful framework into which quantitative relationships may be placed to provide guidance in reaching water quality goals. Existing, state-of-the-art media-specific toxic organic transport and fate models for atmospheric (DiDOT), land surface (NPS) and surface water processes (EXAMS) and potable water treatment (WTP) have been linked to demonstrate the technical feasibility of such an approach. Limited application and sensitivity testing of this linked modeling system has shown that the impact of various source loadings and control strategies on drinking water quality can be estimated.     

Patients' attitudes following chorionic villus sampling

The attitudes of 190 patients who had undergone chorionic villus sampling (CVS) were assessed by means of a questionnaire. One hundred and fifty-two patients replied of whom 68 (45 per cent) were referred because of increased maternal age and in the other 84 cases the indications included previous chromosomal abnormalities, fetal sexing, DNA analysis, and biochemical analysis. One hundred and twenty-two patients had a transcervical procedure, 24 had a transabdominal, and six patients required both procedures. One hundred and forty-one patients (93 per cent) reported CVS to be a satisfactory procedure, and the same percentage thought earlier diagnosis was beneficial. Thirty-nine patients (81 per cent) reported a better experience with CVS than with a previous amniocentesis. A majority of patients (93 per cent) wished a CVS in a future pregnancy and 137 patients (97 per cent) would accept a risk of miscarriage from the procedure of twice that quoted for amniocentesis (1 per cent).     

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.