Exploring data quality for some inorganic and organic constituents of inhalable particulate matter (PM10)

Quality assurance (QA) assessments of air pollution data sets provide a basis for evaluating the significance of various substances in the atmosphere. For non-criteria pollutants, QA results are seldom reported in the technical literature and are often difficult to estimate. The present report provides a summary of QA results such as recovery, precision and accuracy data. Of the six trace elements and nine organic constituents compared in detail, recoveries, laboratory precision and laboratory accuracy values were 100%, ±3% to ±19% and-2 to-13% for the former group and 69% to 98%, ±7% to 23% and-15 to-34% for the later group. System precision varied from ±22% to ±47% for the trace elements and ±42% to ±83% for the organic constituents. Limitations in the interpretation of non-criteria particulate-phase pollutant data bases are discussed with some emphasis placed on receptor-modelling and risk assessment applications. Finally, the relevance of NBS certified materials for QA estimates in non-criteria air pollutant studies is also reviewed.     

Human plasma levels of POPs,and diet among native people from Uelen,Chukotka

Some of the people living in the Chukotka Peninsula of Russia depend heavily on marine mammals, but little is known of the exact dietary patterns and plasma levels of POPs among these populations. In this study, POPs levels in plasma from 50 participants from the isolated community of Uelen (Bering Strait) were determined and related to dietary information obtained through a food frequency questionnaire. The intake of marine mammals was high and the combined intake of blubber from walrus, seal and whale was a significant predictor (p < 0.01) of plasma concentrations of sum PCBs and borderline for sum CDs (p = 0.02) and sum DDTs (p = 0.04). There was a significant gender difference in the levels of POPs, and among women there was a significant increase with age. Extensive breastfeeding and lower blubber intake among women could be possible explanations for this gender difference. Despite the high intake of blubber the plasma levels of PCBs and DDTs were lower than some of those reported for the East Coast of Greenland. The geometric mean values for sum PCBs (17 congeners) and sum DDTs were 1316 ng g(-1) lipids and 563 ng g(-1) lipids, respectively. PCB 163, which partly co-eluted with PCB 138, was found in high concentrations (40% of PCB 138). This raises questions regarding the validity of using PCB 138 and PCB 153 to calculate the level of Arochlor 1260. The geometric mean of sum CDs was 518 ng g(-1) lipids. Concentrations of beta-HCH (geometric mean; 410 ng g(-1) lipids) were higher than observed for other native populations depending on marine mammals. Transportation of beta-HCH by ocean currents through the Bering Strait into the Arctic Ocean or regional point sources might explain these elevated levels.     

Integration of modeling,monitoring and laboratory observation to determine reasons for air quality violations

An attempt was made to explain ambient air quality violations in the vicinity of industrial plants. Micrometeorology, diffusion calculaations, ambient readings, and plant engineering data are all taken into consideration to ascertain whether the plant is or is not the principal offender.Scrutiny of hi-vol filters using scanning electron microscopy for particle size analysis and particle chemical make-up as an assessment technique is also described.Case histories using the above analytical techniques are discussed.Presented at the 16th National Conference on Energy and the Environment, May 23, 1979     

Further studies using X-ray fluorescence to sample lead contaminated carpeted surfaces

The sampling of carpeted surfaces to test for lead contamination primarily focuses upon vacuum techniques. Vacuum sampling techniques, however, require time-consuming, expensive laboratory analysis of the dusts obtained and are unable to determine total lead load on the carpet. X-ray fluorescence (XRF) analysis is an on-site, inexpensive, non-destructive, quick technique for predicting metals levels in a variety of media, such as water, soil, filter paper and painted surfaces. A 1992 study of the feasibility of XRF to analyze for lead and soil loadings on carpeted surfaces indicated that XRF can detect lead at a low enough level to warrant further study. This paper expands this earlier study and developes lead and soil loading calibration curves for three different carpet types based upon XRF lead L-beta peak areas and XRF iron and barium K-alpha peak and background areas. Results indicate that variation in the data can be reduced through modifications of the XRF analysis technique, thus reducing the statistically determined detection level, and that carpet type does affect the calibration. Detection levels of approximately 70 mg/m² for lead and 5 g/m² for soil were obtained. Overall, good agreement was found between results of this study and the earlier one. XRF shows excellent potential for quantitative analysis of lead on carpeted surfaces.     

Criteria for the evaluation of alternative environmental monitoring variables: Theory and an application using winter flounder (Pleuronectes americanus) and Dover sole (Microstomus pacificus)

The design of environmental monitoring programs is frequently hampered by a lack of objective, quantitative criteria for evaluating alternative monitoring variables. In this paper we describe two such criteria, which we call samples required — the number of samples required to detect a given change in value — and information imparted — the amount of environmental information revealed by the monitoring variable. We then use these criteria to evaluate fin erosion in winter flounder (Pleuronectes americanus) and Dover sole (Microstomus pacificus) as marine environmental monitoring variables. Two methods for determining the samples required use contaminated and reference areas to estimate the sample statistics of a hypothetical impacted population. The first method is based on the overall difference in the proportions of diseased fish in the reference and hypothetical populations. The second treats the proportion of diseased fish in individual trawls as the variate and determines the samples required based on the mean and variance of the reference and contaminated populations. We use both methods to predict the number of trawls needed to detect an increase of 200% in fin erosion in the reference population. The first method had greater statistical power but assumes spatially homogeneous populations. The second method accounts for environmental patchiness. For Dover sole it predicted 1661 trawls would be needed to detect the 200% increase. An estuarine winter flounder population would require 74 trawls, and an oceanic winter flounder population would require 142.5 trawls. It appears that fin erosion in winter flounder may be a useful indicator of environmental contamination, but several stipulations apply. Migration may inflate the number of diseased fish observed in the reference population, and a more detailed etiology of the disease is required, including an understanding of what contaminants are responsible for manifestation of the disease.     

Application of a checklist for quality assistance in environmental modelling to an energy model

Large, complex energy models present considerable challenges to develop and test. Uncertainty assessments of such models provide only partial guidance on the quality of the results. We have developed a model quality assistance checklist to aid in this purpose. The model checklist provides diagnostic output in the form of a set of pitfalls for the model application. The checklist is applied here to an energy model for the problem of assessing energy use and greenhouse gas emissions. Use of the checklist suggests that results on this issue are contingent on a number of assumptions that are highly value-laden. When these assumptions are held fixed, the model is deemed capable of producing moderately robust results of relevance to climate policy over the longer term. Checklist responses also indicate that a number of details critical to policy choices or outcomes on this issue are not captured in the model, and model results should therefore be supplemented with alternative analyses.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Soil properties and crop productivity as influenced by flyash incorporation in soil

Field experiments were carried out during 1996–97at Gulawathi, Muthiani and Salarpur Villages, IARI Farm, NewDelhi and NCPP Campus, Dadri to evaluate changes in soilcharacteristics and growth of wheat (Triticum aestivum L.),mustard (Brassica juncea L.), lentil (Lence esculentaMoench.), rice (Oryza sativa L.) and maize (Zea mays L.) byvarying amounts of flyash addition (up to 50t ha^-1) in soils atsowing/transplanting time of crops. Flyash addition in areasadjoining NCPP Thermal Power Plant, Dadri, Ghaziabad, U.P.ranged from 5–12 t ha^-1 yr^-1 in 1995–96. Shoot and root growthand yield of test crops at different locations after flyashincorporation resulted in beneficial effects of flyashaddition in most cases. The silt dominant texture of flyashimproved loamy sand to sandy loam textures of the surfacesoils at the farmers' fields. The increased growth in yield ofcrops with flyash incorporation was possibly due tomodifications in soil moisture retention and transmissioncharacteristics, bulk density, physico-chemical characterssuch as pH and EC and organic carbon content. The response offlyash addition in the soil on soil health and cropproductivity needs to be evaluated on long-term sustainableaspects.     

The Influence of pH on Mobility of Heavy Metals from Municipal Solid Waste Incinerator Fly Ash

Incineration has become one of the principal methods for municipal solid waste disposal particularly in all large cities throughout the world. Currently, the municipal solid waste incinerator fly ashes (MSWIF) are disposed of by landfill. The metal speciation of cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), and zinc (Zn) in MSWIF after been extracted with water at different pH values were examined using a sequential extraction procedure. The extraction sequence was as follows: (1) Exchangeable (NaOAc, pH 8.2), (2) Bound to Carbonates (NaOAc, pH 5.0), (3) Bound to metal oxides (HONH3Cl), (4) Bound to organic matters (HNO3, H2O2), and (5) Residual (HNO3, HCl, H2O2, HF, 1:3:1:3). The heavy metal contents in the extraction solutions were determined by inductively coupled plasma atomic emission spectrometry. The heavy metal concentrations in the different fractions obtained by sequential extraction show distinct distribution trends. The extractable fraction ranges from 25.5 to 88% of the total element content. With the pH of the extractant fall below the neutral and acidic ranges, the concentrations of heavy metals rise substantially due to the released of metals bound to carbonate fraction.