Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

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.     

Utility of dynamics as indicators of stress in population models

The relationships between the dynamics of environmentally and chemically stressed populations and indicators of the effects of the stressor are explored in a model framework. The physiologically structured population, represented by a system of McKendrick–von Foerster hyperbolic partial differential equations, includes the dynamics of numerous individuals distinguished by ecotype. Chemical uptake of nonpolar narcotics is modeled by first order kinetics. Classical methodologies, frequency analysis and phase space reconstruction, are explored in a search for indicators of magnitude of stress. When these techniques proved generally unsuccessful for the objective of indicator selection in our model setting, summary statistics, as related to bifurcation diagrams, were constructed and appear more useful as indicators. It is concluded that physiological structures generally lead to more feasible measurable indicators of magnitude of stress than do specifics of population dynamics.     

Within-and among-clutch variation of organochlorine residues in eggs of black-crowned night-herons

Within-clutch variability of DDE and PCB residues in eggs from 62 clutches of black-crowned night-herons (Nycticorax nycticorax) was small (12% and 17%) compared to among-clutch variability (88% and 83%). Significant correlations between concentrations of DDE (median r=0.8885) and of PCBs (median r=0.8244) occurred when 501 correlations were run on two randomly selected eggs from within the same clutch; no significant correlation occurred for either concentrations of DDE (median r=0.0353) or PCBs (median r=–0.0843) when eggs were not restricted to the same clutch but were restricted to the same colony. The probability of finding infrequently detected organochlorine contaminants (e.g., DDT, cis-chlordane) in eggs from the same clutch varied from 43–96% and increased as the chemical became more prevalent and the number of eggs per clutch became smaller. These results further support one of the basic assumptions of the sample egg technique, that the chemical residues in one egg in a clutch accurately reflect residues in the remaining eggs of the clutch.     

Sampling and analysis for radon-222 dissolved in ground water and surface water

Radon-222 is a naturally occurring radioactive gas in the uranium-238 decay series that has traditionally been called, simply, radon. The lung cancer risks associated with the inhalation of radon decay products have been well documented by epidemiological studies on populations of uranium miners.The realization that radon is a public health hazard has raised the need for sampling and analytical guidelines for field personnel. Several sampling and analytical methods are being used to document radon concentrations in ground water and surface water worldwide but no convenient, single set of guidelines is available. Three different sampling and analytical methods-bubbler, liquid scintillation, and field screening-are discussed in this paper. The bubbler and liquid scintillation methods have high accuracy and precision, and small analytical method detection limits of 0.2 and 10 pCi/l (picocuries per liter), respectively. The field screening method generally is used as a qualitative reconnaissance tool.     

Triploid fetus: An important consideration in the evaluation of very high maternal serum alpha-fetoprotein

Two patients referred for evaluation of very high maternal serum alpha-fetoprotein (10–20 multiples of the median) were carrying triploid fetuses with placentas showing features of partial hydatidiform mole. The diagnosis of fetal triploidy should be considered when there is a very high maternal serum alpha-fetoprotein and no ultrasound evidence of open neural tube defect, ventral wall defect, or any other explanation. Therefore, chromosomal analysis of amniotic fluid cells in such cases is essential.     

Methods for project-based mechanisms (JI/CDM)—relevance of IPCC inventory guidelines

A baseline for a project consists of estimates of annual emissions of greenhouse gases (GHG) for a given time period without implementing the project. A general three-step process for determining the baseline is suggested. The emission reduction of the project is given by the difference between the baseline and the monitored annual emissions. A preferred method, direct measurement of the emission reduction, is possible for some types of projects. Methods for estimating the annual baseline emissions are not necessary for the latter category, and a definition of this project category is suggested. IPCC Guidelines for National GHG Inventories categorise the emission sources so that only direct emissions from consumption of fuel and feedstock are calculated. There are thus no emission factors for indirect emissions (e.g. electricity consumption or km transported) or emission factors that depend on technology only, independent of consumption of fuel and feedstock. Technology-dependent emission factors may thus need to be developed for estimating indirect emissions and multi-project baselines. Consistency should be sought with the IPCC Guidelines when estimating annual baseline emissions and in monitoring project emissions to ensure comparability with the National Inventories.