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.     

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.     

A Watershed-based Cumulative Risk Impact Analysis: Environmental Vulnerability and Impact Criteria

Swine Concentrated Animal Feeding Operations (CAFOs) have received much attention in recent years. As a result, a watershed-based screening tool, the Cumulative Risk Index Analysis (CRIA), was developed to assess the cumulative impacts of multiple CAFO facilities in a watershedsubunit. The CRIA formula calculates an index number based on: 1) the area of one or more facilities compared to the area of the watershed subunit, 2) the average of the environmental vulnerability criteria, and 3) the average of the industry-specific impact criteria. Each vulnerability or impact criterion is ranked on a 1 to 5 scale, with a low rank indicating low environmental vulnerability or impact and a high rank indicating high environmental vulnerability or impact. The individual criterion ranks, as well as the total CRIA score, can be used to focus the environmental analysis and facilitate discussions with industry, public, and other stakeholders in the Agency decision-making process.     

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.     

a study of the temporal variability of atrazine in private well water. part ii: analysis of data

In 1988, the Iowa Department of Natural Resources, along withthe University of Iowa, conducted the Statewide Rural WellWater Survey, commonly known as SWRL. A total of 686private rural drinking water wells was selected by use of aprobability sample and tested for pesticides and nitrate. A subsetof these wells, the 10% repeat wells, were additionally sampledin October, 1990 and June, 1991. Starting in November, 1991,the University of Iowa, with sponsorship from the United StatesEnvironmental Protection Agency, revisited the 10% repeat wellsto begin a study of the temporal variability of atrazine and nitratein wells. Other wells, which had originally tested positive foratrazine in SWRL but were not in the 10% population, wereadded to the study population. Temporal sampling for a year-long period began in February of 1992 and concluded in Januaryof 1993. All wells were sampled monthly, a subset was sampledweekly, and a second subset was sampled for 14 day consecutiveperiods. Of the 67 wells in the 10% population tested monthly,7 (10.4%) tested positive for atrazine at least once during theyear, and 3 (4%) were positive each of the 12 months. Theaverage concentration in the 7 wells was 0.10 µg/L. Fornitrate, 15 (22%) wells in the 10% repeat population monthlysampling were above the Maximum Contaminant Level of 10 mg/L at least once. This paper, the second of two papers on thisstudy, describes the analysis of data from the survey. The firstpaper (Lorber et al., 1997) reviews the study design, theanalytical methodologies, and development of the data base.     

Organochlorine and mercury residues in Swainson's and ferruginous hawk eggs collected in North and South Dakota, 1974–79

Residues of organochlorine pesticides, polychlorinated biphenyls (PCBs), and mercury were measured in eggs of Swainson's hawks (Buteo swainsoni) and ferruginous hawks (B. regalis) collected in North and South Dakota during 1974–79. DDE was the most common compound detected in the eggs, but residues were below levels known to have adverse effects on reproduction. Other organochlorine compounds and mercury were found at low levels. Eggs of ferruginous hawks tended to contain more compounds with higher residues than eggs of Swainson's hawks.     

Second derivative spectroscopy for the determination of volatilized ammonia from urea-amended soil

A second derivative spectrometer custom fitted with a 1 m stainless steel White cell and maintained at 105°C is used to make real-time measurements of volatilized NH₃ from urea-amended soil. Comparison of the technique to impinger data shows a 5–16% discrepancy between the two techniques; however, other experiments presented suggests that this is not real. Sulfur dioxide and nitrous oxide interferences are discussed, though they were not found to be present in this study. Instrument response time is shown to be fast if 67% of the total response is achieved in less than 5 min. Fast response is achieved for ammonia if wall-adsorption effects are minimal and if ammonia mass flow is maintained at 0.2 μg min^-1.     

Environmental monitoring of historical change in arsenic deposition with tree bark pockets

ICP-MS analysis recorded historical change (c. 1846 to 2002) in the arsenic concentration of bark included within the trunks (tree bark pockets) of two Japanese oak trees (Quercus crispula), collected at an elevated location approximately 10 km from the Ashio copper mine and smelter, Japan. The arsenic concentration of the bark pockets was 0.016 +/- 0.003 microg cm(-2) c. 1846 (n = 5) and rose 50-fold from c. 1875 to c. 1925, from approximately 0.01 to 0.5 microg cm(-2). The rise coincided with increased copper production in Ashio from local sulfide ores, from 46 tons per year in 1877 to 16,500 tons per year in 1929. Following a decline in arsenic concentration and copper production, in particular during the Second World War, a second peak was observed c. 1970, corresponding to high levels of production from both local (6,000 tons per year) and imported (30,000 tons per year) ores, smelted from 1954. Compared to the local ores, the contribution of arsenic from imported ores appeared relatively low. Arsenic concentrations declined from c. 1970 to the present following the closure of the mine in 1974 and smelter in 1989, recording 0.058 +/- 0.040 microg cm(-2) arsenic (n = 5) in surface bark collected in 2002. The coincident trends in arsenic concentration and copper production indicated that the bark pockets provided an effective record of historical change in atmospheric arsenic deposition.