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.     

Response of the Ascorbate-Peroxidase of Selenastrum capricornutum to Copper and Lead in Stormwaters

The green alga Selenastrum capricornutum expresses a uniqueascorbate peroxidase, that responds to copper and lead. Attemptswere made to test if this peroxidase could be used to monitor thelevels of copper and lead in natural waters. When S.capricornutum was exposed to a stormwater sample, the specificactivity of the peroxidase in the cell extract was commensuratewith the combined copper and lead contents in the sample. Theperoxidase responses were also correlated with the 96 hr biomasstoxicity assay of S. capricornutum. However, unlike thebiomass toxicity assay, the peroxidase activity was not affectedby the anions in the samples. The use of this peroxidase can beused as a marker for testing heavy metal toxicity in the water.     

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.     

Monitoring of Seasonal Vegetables for Pesticide Residues

Market samples (60) of six seasonal vegetables were monitoredduring 1996–1997 to determine the magnitude of pesticidalcontamination. The estimation of insecticide residuesrepresenting four major chemical groups i.e. organochlorine,organophosphorous, synthetic pyrethroid and carbamate, was doneby adopting a multiresidue analytical technique employingGC-ECD and GC-NPD systems with capillary columns. The testedsamples showed 100% contamination with low but measurableamounts of residues. Among the four chemical groups, theorganophosphates were dominant followed by organochlorines,synthetic pyrethroids and carbamates. About 23% of the samplesshowed contamination with organophosphorous compounds abovetheir respective MRL values. More extensive studies coveringdifferent regions of Haryana state are suggested to get a clearidea of the magnitude of vegetable contamination with pesticideresidues.     

Should foliar cadmium concentrations be expressed on a dry weight or dry ash weight basis?

Foliar analysis is a valuable tool for evaluating the pollution status of forests. However, the use of foliar diagnosis in large-scale surveys is a complicated process owing to the high variability within the crown. The method used to express foliar concentrations has often been found to diminish the variability. The effect of the method used to express element concentrations on the spatial variability of cadmium (Cd) in the leaves of crack willow (Salix fragilis L.) was investigated by sampling the leaves of one willow at 292 locations in the crown, each sampling location having a volume of 0.027 m3 (0.3 m x 0.3 m x 0.3 m). Cadmium showed a distinct spatial trend in the crown of the tree. Concentrations as low as 2.4 mg kg(-1) dry weight (DW) or 23.1 mg kg(-1) dry ash weight (DAW) were obtained in the top of the crown, and 10.6 mg kg(-1) DW or 73.0 mg kg(-1) DAW in the bottom of the crown. The lower relative standard deviation and weaker correlation with the sampling height support the use of DAW in large-scale surveys especially. The lower variability of the DAW Cd concentration makes this variable less sensitive to fluctuations caused by differences in growing conditions and sampling methodology. However, the majority of publications in this field report metal concentrations on a DW basis. Therefore, the restrictions set on the use of results expressed on a DAW basis in large-scale surveys of foliar metal concentrations have to be offset against the advantages offered by a reduction of the variability in metal concentrations.     

Identification of dredged sediment-derived soils in the alluvial plains of the Leie and the Upper and Sea Scheldt rivers (Belgium) based on physico-chemical soil properties

An approach was developed to identify surface soils affected by historical dredged sediment disposal in the alluvial plains of the Upper Scheldt, the Sea Scheldt and the Leie river. Dredged sediment-derived soils were identified based on field observations, comparative granulometric analyses and chemical analyses. Criteria developed were based on a comparison between reference data from 102 aerobic soil samples of areas known to be affected by dredged sediment disposal and 104 samples from undisturbed alluvial soils along the studied rivers. A comparative grain size analysis with optical laser diffractometry between the A and C horizon proved useful for the identification of levelled-up sites. The chemical soil characteristics that were most useful in identifying dredged sediment-derived soils were CaCO3, sulfur (S), organic carbon (OC) and phosphorus (P) contents, electrical conductivity (EC), and the C/P and C/S ratios. Criteria for concluding the origin of an investigated soil were specific for the studied area, but the approach presented may provide useful guidelines for developing criteria valid for different regions.     

Isotopic characterisation of lead deposited 1989-2001 at two upland Scottish locations

The isotopic composition of lead collected with grass samples taken over the period 1989-2001 from plots at two upland locations (Glensaugh in north east and Hartwood in central Scotland) has been determined using thermal ionisation mass spectrometry. Although marked reductions in lead concentrations in grass were observed at Glensaugh in the initial three years, subsequently concentrations have remained relatively constant (1-3 microg g(-1)) in all plots to the present day. The one exception was a roadside plot at Hartwood which showed a large reduction from 1.0 microg g(-1) in 1999 to 0.2 microg g(-1) in 2000 following the abolition of petrol lead in the UK at the beginning of 2000. The total concentrations at this plot were consistently lower than those found at plots away from road traffic but exposed to the prevailing wind direction. The 206Pb/207Pb ratio increased steadily at all the plots throughout the period of the study indicating the reducing influence of petrol lead but the changes were not as great as might be expected with the decrease in the use of leaded petrol. Assuming the collected lead had only two sources, petrol lead and a diffuse background "industrial" lead, the proportion of petrol lead was only in the range 17-69% for roadside samples and 0-39% in other samples. A substantial proportion of deposited lead, therefore, now has its origin other than in petrol. Mixing curves indicate that whereas the lead deposited at Glensaugh could be defined by only two end members, that at Hartwood needs more than two components in the mixture. The results also suggest that although petrol lead has been eliminated, traffic is still a source of lead and another source defined as "traffic lead" should be considered.     

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.     

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.