Further studies using X-ray fluorescence to sample lead contaminated carpeted surfaces

The sampling of carpeted surfaces to test for lead contamination primarily focuses upon vacuum techniques. Vacuum sampling techniques, however, require time-consuming, expensive laboratory analysis of the dusts obtained and are unable to determine total lead load on the carpet. X-ray fluorescence (XRF) analysis is an on-site, inexpensive, non-destructive, quick technique for predicting metals levels in a variety of media, such as water, soil, filter paper and painted surfaces. A 1992 study of the feasibility of XRF to analyze for lead and soil loadings on carpeted surfaces indicated that XRF can detect lead at a low enough level to warrant further study. This paper expands this earlier study and developes lead and soil loading calibration curves for three different carpet types based upon XRF lead L-beta peak areas and XRF iron and barium K-alpha peak and background areas. Results indicate that variation in the data can be reduced through modifications of the XRF analysis technique, thus reducing the statistically determined detection level, and that carpet type does affect the calibration. Detection levels of approximately 70 mg/m² for lead and 5 g/m² for soil were obtained. Overall, good agreement was found between results of this study and the earlier one. XRF shows excellent potential for quantitative analysis of lead on carpeted surfaces.     

Factor analysis of trace-element data from tree-bark samples in The Netherlands

Monte Carlo-assisted factor analysis has been applied to a data set of 20 trace-element concentrations in tree-bark samples obtained from 123 locations in The Netherlands, with the aim to investigate the suitability of bark as a biomonitor for air pollution. A Monte Carlo approach was used to give more insight to the uncertainties and significance levels of the factor analysis results. Notwith-standing a rather strong influence of soil material on the concentration levels, factor analysis enabled the identification of five significant pollution source types, all of which corresponded with source types found in an earlier biomonitoring study in The Netherlands using epiphytic lichens. A more detailed comparison with the lichen results showed a remarkable difference in lead concentrations between bark and lichen. It was concluded that bark can be successfully employed as a biomonitor for air pollution. The power of factor analysis to adequately determine the soil contribution may render extensive sample washing procedures superfluous.     

Ambient air concentrations of PCDDs,PCDFs, coplanar PCBs,and PAHs at the Mississippi Sandhill Crane National Wildlife Refuge,Jackson County,Mississippi

Our objective was to determine the levels of selected airborne contaminants in ambient air at the Mississippi Sandhill Crane National Wildlife Refuge, Mississippi, that might be affecting the health of endangered cranes living there. Two high-volume air samplers were operated at separate locations on the Refuge during May–September 1991. The sampling media were micro-quartz filters in combination with polyurethane foam plugs. Composite bimonthly samples from each station were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Overall, residue concentrations were low. The toxic PCDD isomer 2,3,7,8-tetra-CDD was not detected, nor was penta-CDD. There was no difference (P>0.05) in residue concentrations between stations or over time and meteorological parameters were not correlated with residue concentrations. Because contaminant levels and patterns may differ seasonally, we recommend that air samples collected during winter months also be analyzed for these same chemical groups.     

Organochlorine contaminant concentrations in caddisfly adults (Trichoptera) collected from great lakes connecting channels

Pennsylvania-style light traps were used to capture adult Trichoptera from the St. Marys, St. Clair, Detroit and Niagara rivers, Canada. Adequate biomass was acquired in single, 2-h collections to permit triplicate gas chromatographic analyses of 1–4 g samples for 36 organochlorine contaminants. Contaminant levels varied unpredictably but relatively little among samples taken at monthly intervals over the summer. Samples collected simultaneously from the two sides of the Detroit R. reflected local sediment contaminant patterns, suggesting limited dispersal by adults. Genus-specific differences in contaminant concentrations within the Hydropsychidae and Leptoceridae probably reflect differences in larval habitats and manner of feeding. Contaminant concentrations and relative composition paralleled published reports of contaminants in sediments from collection locations. St. Marys R. caddisflies contained contaminant levels indistinguishable from samples collected at reference sites. St. Clair R. samples contained high levels of compounds associated with petrochemical industries located in the river's upstream reaches. High levels of polychlorinated biphenyls (PCBs) and most other contaminants in Detroit R. samples reflected industrial loadings near Detroit, Michigan. Niagara R. samples contained elevated concentrations of PCBs and pesticides. Cluster analysis grouped samples into five clusters each with unique contaminant composition. These also corresponded to geographic origin: St. Marys, St. Clair, Detroit and upper and lower Niagara rivers. The relative ease of collection and consistent results obtained render adult Trichoptera potentially valuable candidates for surveys of aquatic contamination over a broad range of geographical and ecological conditions.     

Multimedia environmental monitoring: 50 years at Hanford

Environmental monitoring has been an ongoing activity on the U.S. Department of Energy's Hanford Site in southeastern Washington for almost 50 years. Objectives are to detect and assess potential impacts of Site operations on air, surface and ground waters, foodstuffs, fish, wildlife, soil and vegetation. Data from monitoring effects are used to calculate the overall radiological dose to humans working onsite or residing in nearby communities. In 1989, measured Hanford Site perimeter concentrations of airborne radionuclides were below applicable guidelines. Concentrations of radionuclides and nonradiological water quality in the Columbia River were in compliance with applicable standards. Foodstuffs irrigated with river water taken downstream of the Site showed radionuclide levels that were similar to those found in foodstuffs from control areas. Low levels of ¹³⁷Cs and ⁹⁰Sr in most onsite wildlife samples and concentrations of radionuclides in soils and vegetation from on- and offsite locations were typical of those attributable to worldwide fallout. The calculated dose potentially received by a maximally exposed individual (i.e., based on hypothetical, worst-case assumptions for all routes of exposure) in 1989 (0.05 mrem/yr) was similar to those calculated for 1985 through 1988.In addition to monitoring radioactivity in fish and wildlife, population numbers of key species are determined. Chinook salmon (Oncorhynchus tshawytscha) spawning in the Columbia River at Hanford has increased in recent years with a concomitant increase in winter roosting activity of bald eagles (Haliaeetus leucocephalus). An elk (Cervus elaphus) herd, established by immigration in 1972, is also increasing. The Hanford Site currently serves as a refuge for Canada goose (Branta canadensis), great blue heron (Ardea herodias), and various plants and other animals, e.g., mule deer (Odocoileus hemionus), and coyotes (Canis latrans).     

Trend evaluation of water quality parameters in the Niagara and St. Lawrence Rivers

Physical and chemical (nutrients and major ions) indicators of water quality monitored by Environment Canada between 1977 and 1987 in the Niagara River at Niagara-on-the-Lake and in the St. Lawrence River at Wolfe Island are analyzed for seasonal and annual variations. Parametric methods such as moving averages and linear regression and nonparametric methods (Spearman's rank coefficient) are used to test for the existence of trends in these data. The results indicate that specific conductivity, sodium and chloride have decreased significantly over the period of study. During the same period there is no significant trend for either discharge and nutrients.     

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).     

Soil properties and crop productivity as influenced by flyash incorporation in soil

Field experiments were carried out during 1996–97at Gulawathi, Muthiani and Salarpur Villages, IARI Farm, NewDelhi and NCPP Campus, Dadri to evaluate changes in soilcharacteristics and growth of wheat (Triticum aestivum L.),mustard (Brassica juncea L.), lentil (Lence esculentaMoench.), rice (Oryza sativa L.) and maize (Zea mays L.) byvarying amounts of flyash addition (up to 50t ha^-1) in soils atsowing/transplanting time of crops. Flyash addition in areasadjoining NCPP Thermal Power Plant, Dadri, Ghaziabad, U.P.ranged from 5–12 t ha^-1 yr^-1 in 1995–96. Shoot and root growthand yield of test crops at different locations after flyashincorporation resulted in beneficial effects of flyashaddition in most cases. The silt dominant texture of flyashimproved loamy sand to sandy loam textures of the surfacesoils at the farmers' fields. The increased growth in yield ofcrops with flyash incorporation was possibly due tomodifications in soil moisture retention and transmissioncharacteristics, bulk density, physico-chemical characterssuch as pH and EC and organic carbon content. The response offlyash addition in the soil on soil health and cropproductivity needs to be evaluated on long-term sustainableaspects.     

Using environmental stressor information to predict the ecological status of Maryland non-tidal streams as measured by biological indicators

In Maryland, U.S., an interim framework has recentlybeen developed for using biologically based thresholds, or `biocriteria', to assess the health of nontidal streams statewide at watershed scales. The evaluation of impairment is based on indices of biological integrity from the Maryland Biological Stream Survey (MBSS). We applied logistic regression to quantify how the biotic integrity of streams at a local scale is affected by cumulative effects resulting from catchment land uses, point sources, and nearby transmission line rights-of-way. Indicators for land use were developed from the remote sensing National Land Cover Data and applied at different scales. We determined that the risk of local impairment in nontidal streams rapidly increases with increased urban land use in the catchment area. The average likelihood of failing biocriteria doubled with every 10% points increment in urban land, thus an increase in urban land use from 0 to 20% quadruples the risk of impairment. For the basins evaluated in this study, catchments with more than 40–50% urban land use had greater than 80% probability of failing biocriteria, on average. Inclusion of rights-of-way and point sources in the model did not significantly improve the fit for this data set, most likely because of their low numbers. The overall results indicate that our predictive modeling approach can help pinpoint stream ecosystems experiencing or vulnerable to degradation.     

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)).