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.     

Formation and Emission of N2O and CH4 from Compost Heaps of Organic Household Waster

Composting can be a source of N₂O andCH₄ production. In this investigation, differentcompost heaps of organic household waste weremonitored with the focus on potential formation ofCH₄ and N₂O in the heaps and emission ofthese gases from the heaps. The studied compost heapshad different compost ages, turning intervals andcompost sizes. The analysed compost gases containedbetween 1–3421 L of N₂O-N L^-1 and 0–470 mL of CH₄ L^-1. The emission rates ofN₂O and CH₄ from the compost heaps werebetween 1–1464 mg N₂O m^-2 day^-1 and0–119 000 mg CH₄ m^-2 day^-1. These verylarge differences in compost gas composition andemission indicate the importance of compostmanagement. The results also give an understanding ofwhere in the composting process an increasing emissionof N₂O and CH₄ can occur.     

The collection of PM10 for toxicological investigation: comparisons between different collecting devices

A positive correlation has been established between increased levels of airborne particulate pollution and adverse health effects, the toxicological mechanisms of which are poorly understood. For toxicologists to unambiguously determine thesemechanisms, truly representative samples of ambient PM₁₀ are required. This presents problems, as PM₁₀ collecting equipment commonly employed, such as the Tapered Element Oscillating Microbalance (TEOM®), heat the inflow toexclude moisture or use fibrous filters, resulting in a PM₁₀sample that may have undergone significant chemical change on thefilter surface or is contaminated by filter fibres. Other systems(i.e. Negretti and Partisol) can successfully collect PM₁₀ without chemical alteration or filter contamination. Comparativecollections from Port Talbot, S. Wales suggest that TEOMs and Negretti/Partisol systems collect different PM₁₀'s; the principle difference arising from the TEOM's heating chamber, which precipitates water-soluble ions and volatilises some organic components. This results in both the mass and compositionof the PM₁₀'s being altered. Particle size distributionsfor Negretti and Partisol collections highlighted differences mainly attributed to different flow rates. The results of thiswork demonstrate that simple correlations between PM₁₀ massand adverse health effects are problematic. Furthermore, elucidation of the complex fractionation and chemical changes indifferent collectors is necessary.     

On-line solid phase extraction with polyurethane foam: trace level spectrophotometric determination of iron in natural waters and biological materials

This paper reports the development of a simple and accurate on-line procedure for preconcentration and determination of dissolved iron in waters and biological materials using unloaded polyether-type polyurethane foam as solid extractor. In the developed flow injection system, the analyte was preconcentrated from acidic aqueous medium as iron-thiocyanate complex with post-elution with ascorbic acid solution and spectrophotometric measurement with 1,10-phenanthroline as colorimetric reagent. In order to improve the performance of the system several chemical and flow variables were investigated as well as the effect caused by the presence of possible interferents. The method was validated by the analysis of two certified reference materials. Application of the methodology was carried out by the determination of dissolved iron content in eight natural water samples with different characteristics. The results were compared with those obtained by electrothermal atomic absorption spectrometry (ETAAS) and no statistical difference was observed. The detection limit was 0.75 microgram l-1 and the RSD was 1.2% for 2 min preconcentration time. At this condition, a productivity of 20 samples h-1 was achieved. Increasing the preconcentration time up to 3 min, a detection limit of 0.45 microgram l-1, an RSD of 1.5% and an analytical throughput of 15 h-1 were verified.     

Application of intrawell testing of RCRA groundwater monitoring data when no upgradient well exists

A statistical quality control approachto detect changes in groundwater quality from aregulated waste unit is described. The approachapplies the combined Shewhart-CUSUM control chartmethodology for intrawell comparison of analyteconcentrations over time and does not require anupgradient well. A case study from the U.S.Department of Energy's Hanford Site is used forillustration purposes. This method is broadlyapplicable in groundwater monitoring programs wherethere is no clearly defined upgradient location, thegroundwater flow rate is exceptionally slow, or wherea high degree of spatial variability exists inparameter concentrations. This study also indicatesthat the use of the Data Quality Objectives (DQO)process can assist in designing an efficient andcost-effective groundwater monitoring plan to achievethe optimum goal of both low false positive and lowfalse negative rates (high power).     

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 Study on Transfer Factors of 60Co and 65Zn from Soil to Plants in the Tropical Environment of Bangladesh

Soil to plant transfer factor (TF) of⁶⁰Co and ⁶⁵Zn was determined fromradioisotope experiments on plants grown in pots underoutdoor ambient tropical conditions for three growingseasons (1995–1998). The TFs were obtained fordifferent plants/crops such as, rice, bean, peanutspineapple, cabbage, tomato, spinach and grass. Theaverage TF values of ⁶⁰Co are found to be 0.087,0.15, 0.12, 0.67, 0.28, 0.79, 1.03 and 0.34respectively for the above mentioned plants/crops. Incase of ⁶⁵Zn, the average TF values are found tobe 2.24, 1.17, 0.89, 1.09, 0.78, 1.34, 2.92 and 1.78,respectively, for the above mentioned plants/crops. Thedata will be useful to assess the radiation exposureto man associated with the releases of radionuclidesfrom nuclear facilities by means of radiologicalassessment models that require transfer factors asinput parameters to predict the contamination ofradionuclides in foodchain.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.     

Air pollution exposure monitoring and estimation. Part VI. Ambient exposure of adults in an industrialised region

This paper presents methodology and results of a dynamic individual air pollution exposure model (DINEX) that calculates the hourly exposure for each adult in a panel study. Each of over 260 participants, through the use of a diary, provided information used in the model to calculate his/her personal, individualised exposure. The participants filled out the diary daily, hour by hour, over two, two month periods. The exposure assessment model coupled the diary information and results of an indoor/outdoor measurement program, with the results of dispersion modelling on an hourly basis for an industrial area in Norway. The estimated air pollution concentrations from the dispersion model, based on continuous meteorological measurements, were calibrated with air pollutant concentrations measured continuously.