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.     

Monitoring atmospheric metal pollution: a review of the use of mosses as indicators

This article reviews the literatureon the use of mosses for monitoring atmospheric metalpollution. It discusses the nature of mosses, themechanisms for moss uptake of metals from the air andwet precipitation, the various forms in which mossesare used for this purpose, and cases in which mosseshave been used for monitoring local hot spots ofpollution, and regional patterns of metal pollution.Also highlighted are the questions of uptake of metalsfrom the substrates, interspecies differences, and acomparison of the effectiveness of mosses with otherindicator materials, among other issues.     

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).     

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.     

A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

Hydropower production and river rehabilitation: A case study on an alpine river

Despite the numerous benefits of hydropower production, this renewable energy source can have serious negative consequences on the environment. For example, dams act as barriers for the longitudinal migration of organisms and transport of particulate matter. Accelerated siltation processes in the receiving river reduce the vertical connectivity between river and groundwater. Hydropeaks, caused by short-term changes in hydropower operation, result in a negative impact on both habitat and organisms, especially during winter months when natural discharge is low and almost constant. In this study, we report the current deficits present in the River Rhone from two different scientific perspectives – fish ecology and hydrology. Potential rehabilitation solutions in synergy with flood protection measures are discussed. We focus on the effects of hydropeaking in relation to longitudinal and vertical dimensions and discuss local river widening as a potential rehabilitation tool. The fish fauna in the Rhone is characterized by a highly unnatural structure (low diversity, impaired age distribution). A high correlation between fish biomass and monotonous morphology (poor cover availability) was established. Tracer hydrology provided further details about the reduced permeability of the riverbank, revealing a high degree of siltation with K values of about 4.7 × 10^?6 m s^?1. Improving the hydrologic situation is therefore essential for the successful rehabilitation of the Rhone River. To this end, hydropeaks in the river reaches must be attenuated. This can be realized by a combination of different hard technical and soft operational measures such as retention reservoirs or slower up and down ramping of turbines.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

Relevance of radiation compensation litigation to compensation for toxic exposures

Several recent court decisions add to the growing body of law concerning the responsibility of Government in radiation matters and the quantum of proof needed to show causation between radiation exposures and certain types of cancer and leukemia. The courts have also been addressing a wide range of compensation claims for exposures to toxic chemicals with demonstration of causation being a particularly difficult task. Meanwhile, the Congress has been attempting to legislate a far reaching administrative and judicial framework for compensating toxic victims, including an easing of burden-of-proof requirements for demonstrating causation and a broadening of the basis for admissibility of scientific evidence. Drawing parallels between radiation and toxic exposure problems can be both instructive and misleading. Some of the technical issues are quite similar, including the importance of person-specific exposure estimates and of epidemiological studies. However, the uncertainties associated with toxic exposures are usually far greater, and the scientific data base for relating exposures and effects is much more uncertain.