On-line solid phase extraction with polyurethane foam: trace level spectrophotometric determination of iron in natural waters and biological materials

This paper reports the development of a simple and accurate on-line procedure for preconcentration and determination of dissolved iron in waters and biological materials using unloaded polyether-type polyurethane foam as solid extractor. In the developed flow injection system, the analyte was preconcentrated from acidic aqueous medium as iron-thiocyanate complex with post-elution with ascorbic acid solution and spectrophotometric measurement with 1,10-phenanthroline as colorimetric reagent. In order to improve the performance of the system several chemical and flow variables were investigated as well as the effect caused by the presence of possible interferents. The method was validated by the analysis of two certified reference materials. Application of the methodology was carried out by the determination of dissolved iron content in eight natural water samples with different characteristics. The results were compared with those obtained by electrothermal atomic absorption spectrometry (ETAAS) and no statistical difference was observed. The detection limit was 0.75 microgram l-1 and the RSD was 1.2% for 2 min preconcentration time. At this condition, a productivity of 20 samples h-1 was achieved. Increasing the preconcentration time up to 3 min, a detection limit of 0.45 microgram l-1, an RSD of 1.5% and an analytical throughput of 15 h-1 were verified.     

Application of intrawell testing of RCRA groundwater monitoring data when no upgradient well exists

A statistical quality control approachto detect changes in groundwater quality from aregulated waste unit is described. The approachapplies the combined Shewhart-CUSUM control chartmethodology for intrawell comparison of analyteconcentrations over time and does not require anupgradient well. A case study from the U.S.Department of Energy's Hanford Site is used forillustration purposes. This method is broadlyapplicable in groundwater monitoring programs wherethere is no clearly defined upgradient location, thegroundwater flow rate is exceptionally slow, or wherea high degree of spatial variability exists inparameter concentrations. This study also indicatesthat the use of the Data Quality Objectives (DQO)process can assist in designing an efficient andcost-effective groundwater monitoring plan to achievethe optimum goal of both low false positive and lowfalse negative rates (high power).     

An Evaluation of Selenium Concentrations in Water, Sediment, Invertebrates, and Fish from the Republican River Basin: 1997–1999

The Republican River Basin of Colorado,Nebraska, and Kansas lies in a valley which contains PierreShale as part of its geological substrata. Selenium is anindigenous constituent in the shale and is readily leached intosurrounding groundwater. The Basin is heavily irrigated throughthe pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water,sediment, benthic invertebrates, and/or fish were collected from46 sites in the Basin and were analyzed for selenium to determinethe potential for food-chain bioaccumulation, dietary toxicity,and reproductive effects of selenium in biota. Resultingselenium concentrations were compared to published guidelines orbiological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 g L^-1, which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3–5 g L^-1, constituting a moderate hazard. Selenium concentrations in sedimentindicated little to no hazard for selenium accumulation fromsediments into the benthic food chain. Ninety-five percent ofbenthic invertebrates collected exhibited selenium concentrationsexceeding 3 g g^-1, a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 g g^-1selenium, indicating a high potential for toxicity andreproductive effects. However, examination of weight profilesof various species of collected individual fish suggestedsuccessful recruitment in spite of selenium concentrations thatexceeded published biological effects thresholds for health andreproductive success. This finding suggested that universalapplication of published guidelines for selenium may beinappropriate or at least may need refinement for systems similarto the Republican River Basin. Additional research is needed todetermine the true impact of selenium on fish and wildliferesources in the Basin.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.     

Air pollution exposure monitoring and estimation. Part VI. Ambient exposure of adults in an industrialised region

This paper presents methodology and results of a dynamic individual air pollution exposure model (DINEX) that calculates the hourly exposure for each adult in a panel study. Each of over 260 participants, through the use of a diary, provided information used in the model to calculate his/her personal, individualised exposure. The participants filled out the diary daily, hour by hour, over two, two month periods. The exposure assessment model coupled the diary information and results of an indoor/outdoor measurement program, with the results of dispersion modelling on an hourly basis for an industrial area in Norway. The estimated air pollution concentrations from the dispersion model, based on continuous meteorological measurements, were calibrated with air pollutant concentrations measured continuously.     

Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Overstory mortality as an indicator of forest health in California

The interagency Forest Health Monitoring Program involves a network of about 4200 forest plots on a triangular grid across the United States. We present data on recent mortality of trees 27.9 cm diameter from the first three years of measurements in California (1992–1994). Three plot designs were used to collect data representative of a 1-ha stand at each site; the designs differed primarily in total area sampled (0.067, 0.4 and 1.0 ha). Approximately 50 sites were visited each year yielding a total of about 150. Field tallies showed few cases of recent mortality in the smallest plot size. Cumulative distribution functions of recent dead tree densities in the 0.067-ha plots differed significantly from those generated by tallies from entire 1-ha stands. We conclude that an area of 0.067 ha is unsuitable to assess and monitor overstory mortality in Pacific Coast forests.The U.S. government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Spatial analysis and mapping the annual mean concentrations of acidity and major ions in precipitation over the United Kingdom in 1986

The composition of precipitation is being monitored in collectors sited throughout the United Kingdom. In the first year, 1986, hydrogen ion, nitrate, ammonium and non-marine sulphate were measured in samples from 47 sites and annual mean concentrations determined. Spatial analysis based on Regionalized Variable Theory revealed autocorrelation in all four ions and reasonable bounded models were fitted to the sample variogram of all four. These were then used to estimate values of a fine mesh grid by simple kriging, and the estimates were then contoured. The estimation errors were similarly mapped, and both sets of maps are presented. The maps show that concentrations of these ions are greatest in eastern parts of the country, as expected from consideration of European emissions and weather patterns. For the first time estimation errors were also mapped and show how the network could be improved.