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.     

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.     

Metolachlor and chlorothalonil dissipation in gypsum-amended soil

This work focused on the interactive effects of the fungicide chlorothalonil (2,3,4,6-tetrachloro-1,3-benzendicarbonitrile) and gypsum on the persistence of the soil-residual herbicide metolachlor (2-chloro-N-(6-ethyl-o-tolyl)-N-[(1RS)-2-methoxy-1-methylethyl]acetamide). Gypsum application was included due to its widespread use on peanut (Arachis hypogaea). Both agricultural grade gypsum and reagent CaSO₄-2H₂O were tested. A laboratory soil incubation was conducted to evaluate interactive effects. Results indicated 1.5X greater metolachlor half-life (DT₅₀) in soil amended with chlorothalonil (37 d) as compared to control soil (25 d). The two gypsum sources alone increased metolachlor DT₅₀ to about 32 d and with the combination of chlorothalonil and gypsum, DT50 was 50 d, 2-fold greater than the control. Chlorothalonil dissipation was rapid (DT₅₀ < 4d). A possible explanation for metolachlor dissipation kinetics is a build-up of the chlorothalonil intermediate (4-hydroxychlorothalonil) which limited soil microbial activity and depleted glutathione S-transferase (GST) from chlorothalonil detoxification. Further information related to gypsum impacts is needed. Results confirm previous reports of chlorothalonil impeding metolachlor dissipation and showed the gypsum application extended persistence even longer. Farming practices, such as reducing metolachlor application rates, may need to be adjusted for peanut cropping systems where chlorothalonil and gypsum are used.     

Formaldehyde Dose-Response in Healthy Nonsmokers

Industrial, commercial, and domestic levels of formaldehyde exposure range from <0.1 to >5.0 ppm. Irritation of the eyes and upper respiratory tract predominate, and bronchoconstriction is described in case reports. However, pulmonary function and irritant symptoms together have not been assessed over a range of HCHO concentrations in a controlled environment. We investigated dose response in both symptoms and pulmonary function associated with 3-h exposures to 0.0-3.0 ppm HCHO in a controlled environmental chamber. Ten subjects were randomly exposed to 0.0, 0.5, 1.0, and 2.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise and nine additional subjects were randomly exposed to 0.0,1.0,2.0, and 3.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise. Significant dose-response relationships in odor and eye irritation were observed (p < 0.05). Nasal flow resistance was increased at 3.0 ppm (p < 0.01), but not at 2.0 ppm HCHO. There were no significant decrements in pulmonary function (FVC, FEV₁, FEF_25-75%, SGaw) or increases in bronchial reactivity to methacholine (log PD_35SGaw) with exposure to 0.5-3.0 ppm HCHO at rest or to 2.0 ppm HCHO with exercise.     

Removal of Volatile Aliphatic Hydrocarbons in a Soil Bioreactor

Soil removal of propane, isobutane and n-butane from a waste air stream was evaluated in the laboratory and in a prototype soil bioreactor. Laboratory investigations indicated first-order kinetics and the potential to degrade light aliphatic hydrocarbons and trichlorethylene, a compound ordinarily resistant to aerobic biological treatment. The predicted behavior of the bioreactor, based on laboratory studies, agreed closely with the actual behavior of the Reid system. The prototype bioreactor reduced the hydrocarbon concentrations in the air by at least 90percent with a residence time of 15 minutes and a pressure drop of 85 cm of water. The bioreactor functioned well through a range of temperatures, 12°C to 24°C.     

Rotary Kiln Incineration III. An Indepth Study—Kiln Exit/Afterburner/Stack Train and Kiln Exit Pattern Factor Measurements During Liquid CCl4 Processing

Temperature and stable species concentration data are presented from various locations within a full-scale rotary kiln incinerator firing natural gas/carbon tetrachloride/air. The data are being collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop a more sophisticated understanding of and a predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. Non-uniformities in stable species and temperature exist for this particular kiln, at the kiln exit, under certain operating conditions. Flow perturbations from within the kiln were found to persist into the afterburner, but not into the stack. High destruction and removal efficiencies (DRE’s) were achieved under the operating conditions of these tests through adequate secondary combustion processing.     

Rotary Kiln Incineration IV. An Indepth Study— Kiln Exit,Transition and Afterburner Sampling During Liquid CCl4 Processing

Detailed temperature and stable species concentration data are presented from the kiln exit, transition section and afterburner of a full-scale incinerator facility firing natural gas/carbon tetrachloride/air. The data are collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop an understanding and predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. The data demonstrate that nonuniformities in stable species and temperature exist, under certain operating conditions, at the kiln exit in the vertical direction only. Measurements from the transition section indicate that non-uniformities may exist within this region under certain operating conditions. Flow perturbations from within the kiln can persist into the afterburner, although the degree of nonuniformity is substantially reduced compared to either the kiln or transition sections. High destruction and removal efficiencies were achieved under all operating conditions of these tests through a combination of kiln and secondary combustion processing.     

The Importance of Natural Processes in Understanding Ecosystem Change: A Case Study of Limed Lakes

In order to determine what effects human activities have on natural processes, it is important to thoroughly understand those processes. Unfortunately, we know little about what natural processes are operating, and even less about how they have functioned historically. This paper discusses the importance of natural processes in affecting surface water acidification and the necessity for developing quantitative estimates of natural, as well as anthropogenic, contributions to the acidification of surface waters. A review of the literature and the analysis of chemistry data from six limed lakes in New York and Massachusetts have identified a number of possible processes that may play important roles in acidifying surface waters. At present, these processes are poorly understood and require further research. Once we have such knowledge, we will be able to clearly see the effects of human activities on natural processes and modify those activities in ways that will mitigate negative impact in a predictable manner.     

An Intelligent Emissions Controller for Fuel Lean Gas Reburn in Coal-Fired Power Plants

ABSTRACT

The application of artificial intelligence techniques for performance optimization of the fuel lean gas reburn (FLGR) system is investigated. A multilayer, feedforward artificial neural network is applied to model static nonlinear relationships between the distribution of injected natural gas into the upper region of the furnace of a coal-fired boiler and the corresponding oxides of nitrogen (NO_x) emissions exiting the furnace. Based on this model, optimal distributions of injected gas are determined such that the largest NO_x reduction is achieved for each value of total injected gas. This optimization is accomplished through the development of a new optimization method based on neural networks. This new optimal control algorithm, which can be used as an alternative generic tool for solving multidimensional nonlinear constrained optimization problems, is described and its results are successfully validated against an off-the-shelf tool for solving mathematical programming problems. Encouraging results obtained using plant data from one of Commonwealth Edison's coal-fired electric power plants demonstrate the feasibility of the overall approach.

Preliminary results show that the use of this intelligent controller will also enable the determination of the most cost-effective operating conditions of the FLGR system by considering, along with the optimal distribution of the injected gas, the cost differential between natural gas and coal and the open-market price of NO_x emission credits. Further study, however, is necessary, including the construction of a more comprehensive database, needed to develop high-fidelity process models and to add carbon monoxide (CO) emissions to the model of the gas reburn system.