Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.     

profiling areas of ground water contamination by pesticides in california: phase ii – evaluation and modification of a statistical model

A well sampling study was conducted to evaluate anempirical approach to classifying areasof land in California as vulnerable to ground watercontamination by pesticides (Troiano et al., 1994). Wells were sampled from sections of land that had noprevious detections of pesticideresidues. The sections had been classified into vulnerablesoil clusters or into a not-classified groupusing a procedure based on Principal Components Analysis(PCA). Grape, citrus, and olive growingareas of Fresno and Tulare Counties were targeted, areas wherepre-emergence herbicide residues hadbeen detected in well water. Overall, herbicide residues weredetected in 75 of 176 sampled wells, ahigh frequency of detection in relation to results fromprevious targeted well sampling studies. Sinceresidues were also detected in the not-classified group, theclassification procedure was modified usingan approach based on Canonical Variates Analysis (CVA). Moresections were classified intovulnerable soil clusters with the CVA approach than with thePCA method. Data from two otherexplanatory variables, depth to ground water and amount ofpesticide used per section, were includedto illustrate how additional information can be incorporatedinto this approach of identifying vulnerable areas.     

An application of circular-linear correlation analysis to the relationship between Freon concentration and wind direction in Woods Hole,Massachusetts

Two statistical tests for correlation between a circular variate and a linear variate are presented. The tests are applied to a small data set concerning Freon-12 concentration and wind direction in Woods Hole, Massachusetts during the summer of 1987. A significant correlation is found. Further analysis suggests that this directional effect is related to onshore Freon-12 release.Woods Hole Oceanographic Institution Contribution Number 6750     

Estimation of the Thermal Sensitivity of a Dwelling to Variations in Architectural and Behavioural Parameters

The provision of energy for households is a major contributor to greenhouse gas emissions in the domestic sector. There is significant scope for energy savings and thus emission reduction in this sector. This paper constructs a bridge between thermal analysis and environmental assessment in the occupancy stage of the dwelling life cycle, approaching both methods as being on a common system Environment–Dwelling–Inhabitant. The importance of the local level in the thermal analysis and assessment of either a dwelling or an inhabitant's behaviour is demonstrated. It is shown that the researcher can choose between natural experiment, computer experiment and mathematical modelling to analyze the system. Such a choice is discussed for two particular methods of thermal analysis. Thermal Nomograms are the result of mathematical modelling, and the Energy Score Sheet is the result of a computer experiment in energy rating. Despite being developed for the purpose of thermal analysis, these methods can also be utilized for environmental assessment at the local level. The discussion centres on Australian conditions where the majority of the population resides in a relatively benign climate wherein behavioural alterations have significant potential for energy savings and environmental impact. The purpose of the paper is to emphasise benefits apart from energy minimisation to promote the use of energy efficient housing strategies.     

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.     

Field scale variability of cadmium and zinc in soil and barley

CaCl₂-extractable soil Cd and Zn contents have been suggested as a measure of bioavailability. To investigate the ability of this measure to reflect spatial patterns of Cd and Zn concentrations in barley (Hordeum vulgare L.) in an arable field, plant and soil samples were taken from a 0.5 ha area sandy soil contaminated with Cd and Zn. Cd and Zn contents in barley and yield were spatially variable. Yield was low, which may have been caused by Zn toxicity or atrazine turnover. For Cd, CaCl₂-extractable soil contents explained only 17% of the variation in Cd contents in grain, and for Zn no significant correlation was observed. Nevertheless, surface plots of CaCl₂-extractable soil contents and contents of barley grain illustrated their corresponding spatial patterns. Despite the poor linear correlation between CaCl₂-extractable soil-Cd and grain-Cd, a stochastic model for long term behaviour of Cd in field soils predicted observed variability in Cd contents of barley grain well from spatial variability of soil pH and organic matter content. The probabilistic model predicted behaviour of Cd in terms of probability, and was more appropriate than the deterministic approach.     

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.     

Monochlorobenzene Marine Risk Assessment with Special Reference to the Osparcom Region: North Sea

This risk assessment on monochlorobenzene was carried out for the marine environment, following methodology given in the EU risk assessment Regulation (1488/94) and Guidance Document of the EU New and Existing Substances Regulation (TGD, 1996). Data from analytical monitoring programmes in large rivers and estuaries in the North Sea area were collected and evaluated for effects and environmental concentrations. Risk is indicated by the ratio of predicted environmental concentration (PEC) to predicted no-effect concentration (PNEC) for the marine aquatic environment. In total, 27 data for fish, 24 data for invertebrates and 13 data for algae were evaluated. Acute and chronic toxicity studies were taken into account and appropriate assessment factors used to define a final PNEC value of 32 micro/l. Recent monitoring data indicate that monochlorobenzene levels in surface waters are below determination limits of 0.1, 0.2, 0.5 microg/l used in monitoring programs. Assuming that half of the lowest determination (0.1 microg/l) is typical, a PEC of 0.05 microg/l was derived. A worst case of 0.5 microg/l is assumed. PEC/PNEC ratios give safety factors of 60 to over 500, taking no account of dilution in the sea. Monochlorobenzene is not a 'toxic, persistent and liable to bioaccumulate' substance sensu the Oslo and Paris Conventions for the Prevention of Marine Pollution (OSPAR-DYNAMEC) criteria. Environmental fate and effects data indicate that current use of monochlorobenzene poses no unacceptable risk to the aquatic environment.