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.     

Current strategies in nitrite detection and their application to field analysis

The various analytical protocols that have been developed to aid the measurement of nitrite within environmental samples have been critically appraised and their applicability to field measurement assessed. The present communication presents a perspective on current techniques and technologies encompassing spectroscopic, electrochemical and chromatographic methodologies and highlights those that are liable to emerge in the near future. Commercial devices have been included and where appropriate the advantages and limitations posed by their operation within field contexts have been described.     

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.     

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.     

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.     

Excrement from Heron colonies for environmental assessment of toxic elements

Excrement cast from Great Blue Heron nests was collected during the nesting period of 1978 from four colonies in Washington and Idaho. Cheesecloth strips placed on the ground beneath the nests served as excrement collecting devices. Chemical analysis for lead, mercury and cadmium were performed on dried samples. Lead was the most abundant trace metal found in heron debris. The Idaho colony at Lake Chatcolet had an average concentration of 46 ppm in the beneath-nest samples and 6 ppm in control samples. A heron colony near Tacoma, Washington had beneath-nest samples averaging 28 ppm and control samples averaging 20 ppm. Two colonies located in the interior region of Washington had substantially lower concentrations of lead. The difference observed between colonies was attributed to their associations with a polluted watershed (Chatcolet colony) an interstate highway (Tacoma colony) and an unpopulated largely agricultural area (inland Washington).     

Problems of correlation of global and local monitoring of air pollution

1. The Air Polluttion Monitoring System has got a significant development of late, which is in direct relation with a considerable extention and improvement of the observation network in cities and industrial areas, with creation of a new network for assessing regional and global background of the atmosphere pollution, as well as with the wide involvement of meteorologists to monitoring organization.
2. While developing a new global monitoring system, it is necessary to take into account its relationship with the local monitoring within the region of air pollution sources, i.e. at the \lsimpact\rs level. The need in such an account is dictated first of all by the physics of pollutant spreading that states: changes in air pollution over large territories must be in a certain agreement with greater changes in the vicinity of emission sources. Methods applied in the global and local monitoring have also a number of common peculiarities. White organizing regional network for observations of the background pollution of the atmosphere twin stations (one of the pair of stations located outside the city boundaries in a small community, and the other, in the nearest city with the population of 200–400 thousand inhabitants) were established in the U.S.S.R. and in a number of socialist countries in Europe.
3. Implementation of the twin-station principles in the U.S.S.R. has contributed to data interpretation and representativity assessment as well as to correction of the station location. Observation results from the Soviet background stations and those abroad have been compared by now according to a number of indices.
4. The correlation of monitoring systems of various scales tells positively both on mutual improvement and completion of observational methods. The methods of obtaining integral characteristics of air pollution were used for the global monitoring, in particular spectral actinometric observations and chemical analysis of the precipitation composition. Now they find still wider employment. Thus methods of spectral actinometric measurements and data processing were used to estimate the degree of aerosol pollution of a number of industrial centres. The theory of solar radiation spreading and aerosol contents determination in urban atmosphere has also been developed. It is a generalization of an earlier developed theory, used to estimate global atmosphere pollution basing on actinometric data. The organization of precipitation collection and analysis on a network of stations around Leningrad and in Donbass area enables us to compare the admixture content in precipitations falling in industrial and agricultural areas.
5. A considerable increase of possibilities to measure microconcentrations of sulphur dioxide, nitrogen oxides and of a number of other pollutants is connected with the use of solid solvents for sampling. Their use will allow to avoid establishment of special laboratories at background stations and only send samples by post for their analysis in centralized laboratories.

They will also allow to considerably increase precision and accuracy of measurements. The international comparisons of methods of air pollution measurements on the background level allow to judge about the effiency of these methods.