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.     

Luminescence spectroscopy as a screening tool for the potential carcinogenicity of asphalt fumes

A subset of polycyclic aromatic compounds (PACs), which contain 4-6 annulated rings, has been documented as the source of carcinogenicity in animal skin painting studies of petroleum products and asphalt fumes (M. L. Machado, P. W. Beatty, J. C. Fetzer, A. H. Glickman and E. L. McGinnis, Fundam. Appl. Toxicol., 1993, 21, 492; T. A. Roy, S. W. Johnson, G. R. Blackburn and C. R. Mackerer, Fundam. Appl. Toxicol., 1988, 10, 466). Because of the chemical complexity of these materials, it has been difficult to identify the specific compounds within this broad range of PACs responsible for their carcinogenicity. An alternative approach using luminescence spectroscopy was taken in this study to quantify, without identification, a subset of these compounds that appears to cause cancer. The fluorescence response at a specific wavelength pair was obtained for 39 laboratory asphalt fume condensates from animal skin painting studies, yielding a linear correlation coefficient of R2 = 0.96 between the fluorescence response in these materials and the carcinogenicity found in animal studies. In the absence of other asphalt fume condensates from animal studies, 17 petroleum oils were also evaluated using this method and compared with the available animal skin painting data. The details of the method include a clean-up step that removes the highly polar compounds and spectral subtraction of two- and three-ring PAC interference, both of which add to the fluorescence response, yet were not found to contribute to a carcinogenic response from skin painting studies. Full scan fluorescence plots also produce a fingerprint which can be used to assess contamination, such as coal tar products or mixtures of materials, that are not defined as asphalt, yet may be present in the working environment.     

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.     

Assessing the Effects of Atmospheric Ethylene on Epinasty and Tuber Yield of Potato (Solanum Tuberosum L.) Near Polyethylene Manufacturing Plants

A multi-year programme was performed to assess the effects of atmospheric ethylene on potato (Solanum tuberosum L.) in the vicinity of polyethylene manufacturing plants. There was a strong temporal variation of the hourly ethylene concentrations measured close to the sources from 1982 through 1991. Growing seasonal means exceeded 12 g m^–3 ethylene, the threshold for phytotoxic effects under laboratory conditions. Young test plants of potato showed an epinastic response to enhanced levels of ethylene. This response was reversible and did not occur when atmospheric ethylene was not detected. Based on hourly observations for the growing seasons of 1984 through 1991, epinasty occurred on average during circa 5% of the growing season and varied from circa 1% in 1985 to circa 18% in 1991. At night, ethylene concentrations were higher and epinasty was more frequent than during daylight hours. The intermittent exposures to ethylene did not affect tuber yield for the growing seasons of 1982 through 1990. The occurrence of epinasty indicated that ethylene exposure levels in the vicinity of the industrial sources might be sufficiently high to affect sensitive plants.     

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.     

Macroinvertebrate Regionalisation for use in the Management of Aquatic Ecosystems in Victoria, Australia

The development of a broader, more holistic approach to aquaticecosystem management has been called for in recent years. Physical and chemical objectives alone are no longer consideredsufficient for the protection of aquatic ecosystems and shouldbe supplemented with biological objectives. The ubiquitousand sedentary nature of macroinvertebrates, combined with theirmeasurable response to environmental conditions, favour their use as important indicators in environmental policies. To establish biological objectives, there is a need for a regionalframework to limit the variability between ecosystems. Past studies have demonstrated that an a posteriori regionalisationapproach may be more useful than an a priori approach in explaining single component (e.g. macroinvertebrates) patternsacross ecosystems. This is particularly important as aquaticresource management agencies often focus on one or twocomponents of the ecosystem to assess environmental health. This study uses an a posteriori method to delineate and describebiological regions based on edge and riffle macroinvertebrate data. The regionalisation will provide a framework for settingbiological objectives, based on the range of reference conditionsmeasured within each separate region. The objectives will includeregional checklists for taxa and biotic indices. Predictive modelling in the style of RIVPACS or AUSRIVAS will also be usedwithin each region to develop objectives, incorporating local, regional and systematic features as predictor variables.     

Economic and Spatial Impacts of an Existing Reserve Network on Future Augmentation

An optimization model for land reservation was developed that explicitly selects parcels in the most compact or contiguous manner possible while meeting habitat requirements and a budget limitation. The model was used to compare the effects of an existing reserve network on future parcel spatial locations and total cost. Using habitat and land value data from Josephine County, Oregon, it was found that a system of existing reserves created by various policies and overseen by different agencies can decrease future reserve compactness and contiguity, and increase total cost. This work suggests that coordinated planning can result in more efficient conservation efforts for less cost.     

Distribution of Chlorinated Organic Pollutants in Harbor Sediments of Livorno (Italy): A Multivariate Approach to Evaluate Dredging Sediments

Dredging is a very important procedure for harbor management. InItaly the guidelines for the offshore dumping of dredged materials are issued by the Ministry of Environment. Theydescribed a few steps of dredging activities, such as thesampling strategy, but do not deal with limits or guide-valuesfor the chemical, physical and biological composition of theresulting sediments. The quality of dredged materials is mainlydependent on the presence of inorganic and organic pollutants.In particular, polychlorinated biphenyls (PCBs) and organo-chlorinated pesticides are seen as a high priority inmarine environment by international organizations because oftheir persistence, toxicity and bioaccumulation capacity.In this article the presence of some PCBs and organo-chlorinatedpesticides in sediment samples collected from the harbor ofLivorno (Northern Tyrrhenian Sea) was investigated. Theconcentration of HCHs, Aldrin, Chlordanes, DDEs, DDTs, and PCBsin 12 representative sites ranged between <1 g kg^–1and 95, 19, 32, 35, 107, and 111 g kg^–1, respectively.The application of univariate and multivariate statisticaltechniques, such as linear regression analysis and principalcomponent analysis, to the experimental data showed a differentdistribution of PCBs in the two sediment layers. On thecontrary, the vertical distribution of the other investigatedpollutants was more homogeneous and affected by randomvariability. The multivariate approach was an important tool to establish more rational criteria for the management of dredged materials.     

Preliminary air pollution monitoring in San Miguel, Buenos Aires

Passive diffusion samplers were employed in San Miguel(Buenos Aires Metropolitan Area) for a preliminary airpollution monitoring. The highest loads were observedin downtown, compared with an urban background site.Total suspended particulate matter (TSPM) varied from0.257 to 0.033 mg cm^-2 month^-1; dust was examinedfor particle nature and size distribution. A similartrend was observed for nitrogen dioxide (NO₂) andTSPM spatial distribution, suggesting that traffic isthe major pollution source. Sulphur dioxide (SO₂)values were low and rather homogeneous. Levels for theinvestigated pollutants are below EPA's guide linevalues. Geographic (flat area, near to Rio de LaPlata) and climatologic factors (rainfalls andvariable wind directions) contribute to disperse pollutants.     

A Watershed-based Cumulative Risk Impact Analysis: Environmental Vulnerability and Impact Criteria

Swine Concentrated Animal Feeding Operations (CAFOs) have received much attention in recent years. As a result, a watershed-based screening tool, the Cumulative Risk Index Analysis (CRIA), was developed to assess the cumulative impacts of multiple CAFO facilities in a watershedsubunit. The CRIA formula calculates an index number based on: 1) the area of one or more facilities compared to the area of the watershed subunit, 2) the average of the environmental vulnerability criteria, and 3) the average of the industry-specific impact criteria. Each vulnerability or impact criterion is ranked on a 1 to 5 scale, with a low rank indicating low environmental vulnerability or impact and a high rank indicating high environmental vulnerability or impact. The individual criterion ranks, as well as the total CRIA score, can be used to focus the environmental analysis and facilitate discussions with industry, public, and other stakeholders in the Agency decision-making process.