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.     

Use of cluster and principal component analyses to profile areas in California where ground water has been contaminated by pesticides

An empirical approach to profiling areas of ground water contamination by pesticides was devised that did not rely upon determining the level of vulnerability between land areas and that did not assume any particular pathway for ground water contamination. Climatic and soil data were obtained for 1-square mile sections of land in California where pesticide residues had been found in well water samples and the detection was attributed to legal agricultural applications. These sections were designated as known contaminated (KC) sections. Climate and soil data were also obtained for sections which lacked either well sampling data or a positive pesticide detection. These sections were designated as candidate sections. Statistical procedures were used to cluster groups of KC sections first with respect to climate characteristics and then with respect to soil characteristics. Principal components analysis (PCA) was used to construct a statistical profile of soil variables for each cluster of KC sections. A method based on the PCA was developed to compare the similarity of soil profiles derived for each KC section cluster to individual candidate sections. Since the profiling scheme was based only on data from KC sections, candidate sections that did not match any KC cluster profile could only be considered dissimilar to contaminated sections, receiving a status of not-classified. This profiling method is flexible and it can be revised to incorporate updated well sampling information.     

Criteria for the evaluation of alternative environmental monitoring variables: Theory and an application using winter flounder (Pleuronectes americanus) and Dover sole (Microstomus pacificus)

The design of environmental monitoring programs is frequently hampered by a lack of objective, quantitative criteria for evaluating alternative monitoring variables. In this paper we describe two such criteria, which we call samples required — the number of samples required to detect a given change in value — and information imparted — the amount of environmental information revealed by the monitoring variable. We then use these criteria to evaluate fin erosion in winter flounder (Pleuronectes americanus) and Dover sole (Microstomus pacificus) as marine environmental monitoring variables. Two methods for determining the samples required use contaminated and reference areas to estimate the sample statistics of a hypothetical impacted population. The first method is based on the overall difference in the proportions of diseased fish in the reference and hypothetical populations. The second treats the proportion of diseased fish in individual trawls as the variate and determines the samples required based on the mean and variance of the reference and contaminated populations. We use both methods to predict the number of trawls needed to detect an increase of 200% in fin erosion in the reference population. The first method had greater statistical power but assumes spatially homogeneous populations. The second method accounts for environmental patchiness. For Dover sole it predicted 1661 trawls would be needed to detect the 200% increase. An estuarine winter flounder population would require 74 trawls, and an oceanic winter flounder population would require 142.5 trawls. It appears that fin erosion in winter flounder may be a useful indicator of environmental contamination, but several stipulations apply. Migration may inflate the number of diseased fish observed in the reference population, and a more detailed etiology of the disease is required, including an understanding of what contaminants are responsible for manifestation of the disease.     

Heavy metals in the SPM of air in the environment surrounding a ferro-alloy industrial plant in India

Prices for ferro-alloys have hardened due to the closure of plants in developed countries on account of increasingly stringent pollution control legislation, resulting in a higher cost of production. A ferro-alloy industry with a capacity of 80000 MT per annum was selected to study the nature of pollution. Because of the objectionable nature of polluting air in and around the plant it was located in a rural area where there was no other industry. The area was agriculturally active and there was no effective control system for this plant.The quality of ambient air around the plant site is discussed in this paper along with the meteorological conditions. The maximum concentration of suspended particulate matter (SPM) was 768 µg/NM³ downwind of the plant, minimum 184 µg/NM³, and the average was more than 446 µg/NM³. The presence of heavy metals, viz. Fe, Mn, Cr and Pb, was also assessed. The concentration of Fe was 50 µg/NM³ downwind and 10 µg/NM³ upwind. The concentration of other metals followed a similar trend.     

Patchy distributions: Optimising sample size

A method for estimating sample size which does not require an a priori definition of desired precision, or the assumption that the population is normally distributed with constant variance, has recently been proposed. This paper discusses this method and presents five modifications which make the method easier to use and reduce the probability of estimating a larger sample size than is actually required. The method is extended and used to estimate the mean abundance of patchily distributed benthic organisms. The technique can be used to guide the design of any environmental sampling programme, be it physical, chemical or biological, where comparisons between times and/or locations are required. Trade-offs between numbers of replicates and numbers of levels/sites are discussed.     

Distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in soils from the East Antarctic coast

Concentrations of hexachlorobenzene (HCB), alpha-, beta- and gamma-hexachlorocyclohexane (HCH) isomers, 6 o,p'-and p,p'-isomers of DDT and 28 PCB congeners have been measured in eleven soil samples and one lichen collected on the Eastern coast of Antarctica from 5 Russian stations. For samples with low concentrations of PCBs (range 0.20-0.41 ng g(-1) dry weight) and pesticides (0.86-4.69 ng g(-1) and 0.11-1.22 ng g(-1) dry weight for HCHs and DDTs, respectively), atmospheric long-range transport from Africa, South America or Australia was suggested as the sole source of contamination. The profile of PCB congeners was dominated by the more volatile tri-, tetra- and penta-PCBs congeners, thus supporting long-range transport hypothesis. Four samples contained moderate levels of PCBs (range 1.98-6.94 ng g(-1) dry weight) and variable concentrations of pesticides (gamma-HCH, p,p'-DDT and o,p'-DDT being the main contaminants). For samples with high concentrations of PCBs (range 90.26-157.45 ng g(-1)) and high concentrations of pesticides, the presence of high molecular weight PCB congeners such as: 153, 180, 187, 170 etc, strongly suggest a local source (biotic) of PCBs rather than atmospheric transport. It is likely that on a local scale, biotic focussing of pollutants, due to bird activities (nesting and excrement) can cause high contamination levels and become more significant than contaminant input via abiotic pathways.     

Application of PCR and probe hybridization techniques in detection of airborne fungal spores in environmental samples

Specific PCR amplification and probe hybridization techniques were applied to examine the compositions of airborne fungi in samples from three different environments. The results from microscopic and CFU counting were compared to those of the molecular-based detections. The detection sensitivity for PCR amplifications was 9 to 73 spores and 1.3 to 19.3 CFUs per PCR reaction. The hybridization detection limit was 2 to 4 spores and 0.2 to 1.2 CFU. The hybridization method was more sensitive than PCR amplification and showed less variation among samples. Using specific PCR primers and probes we identified the presence of several fungal groups and species in the air samples. Specific detections through probe hybridization to PCR products amplified with universal or group-specific fungal primers have promising applications in the examination of air samples for environmental monitoring.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

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).     

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.