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.     

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.     

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.     

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.     

Nitrogen isotope ratios in pine bark as an indicator of N emissions from anthropogenic sources

The article describes the use of Scots pine bark to identifynitrogen sources in eastern Germany, as well as background areas in Russia and Bulgaria, by using natural isotope ratios of total nitrogen (N_t) and individual N compoundssuch as ammonium (NH₄ ⁺), nitrate (NO₃ ^-)and amid nitrogen (amide-N). The samples collected were analysed using an elemental analyser in connection with a gas isotope mass spectrometer (EA-IRMS). Natural ¹⁵N abundances in pine bark from impact areas suggest that the ammonium accumulated on the surface of the bark is releasedfrom livestock management. Bark of Scots pines growing near agricultural land had highly depleted ¹⁵N_t values (between –8 and –12), while bark from background areas (unpolluted areas) displayed slightly negative ¹⁵N_t values (mean ¹⁵N_t = –3.8). It is assumed that part of the N adsorbed on the bark surface is mainly derived from ammonia(mean ¹⁵N_t = –40.3) escaping from livestock housing and during the application of manure. This assumption is confirmed by experiments under controlled conditions in which manure samples were spread on soil. In addition, temporal and spatial variations of ¹⁵N_t abundances in pine bark from various locations in eastern Germany as wellas pine stands in Nature Park Dübener Heath are discussed.     

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.     

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).