A comparison of portable XRF and ICP-OES analysis for lead on air filter samples from a lead ore concentrator mill and a lead-acid battery recycler

Personal and area samples for airborne lead were taken at a lead mine concentrator mill, and at a lead-acid battery recycler. Lead is mined as its sulfidic ore, galena, which is often associated with zinc and silver. The ore typically is concentrated, and partially separated, on site by crushing and differential froth flotation of the ore minerals before being sent to a primary smelter. Besides lead, zinc and iron are also present in the airborne dusts, together with insignificant levels of copper and silver, and, in one area, manganese. The disposal of used lead-acid batteries presents environmental issues, and is also a waste of recoverable materials. Recycling operations allow for the recovery of lead, which can then be sold back to battery manufacturers to form a closed loop. At the recycling facility lead is the chief airborne metal, together with minor antimony and tin, but several other metals are generally present in much smaller quantities, including copper, chromium, manganese and cadmium. Samplers used in these studies included the closed-face 37 mm filter cassette (the current US standard method for lead sampling), the 37 mm GSP or "cone" sampler, the 25 mm Institute of Occupational Medicine (IOM) inhalable sampler, the 25 mm Button sampler, and the open-face 25 mm cassette. Mixed cellulose-ester filters were used in all samplers. The filters were analyzed after sampling for their content of the various metals, particularly lead, that could be analyzed by the specific portable X-ray fluorescence (XRF) analyzer under study, and then were extracted with acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES). The 25 mm filters were analyzed using a single XRF reading, while three readings on different parts of the filter were taken from the 37 mm filters. For lead at the mine concentrate mill, all five samplers gave good correlations (r2 > 0.96) between the two analytical methods over the entire range of found lead mass, which encompassed the permissible exposure limit of 150 mg m(-3) enforced in the USA by the Mine Safety and Health Administration (MSHA). Linear regression on the results from most samplers gave almost 1 ratio 1 correlations without additional correction, indicating an absence of matrix effects from the presence of iron and zinc in the samples. An approximately 10% negative bias was found for the slope of the Button sampler regression, in line with other studies, but it did not significantly affect the accuracy as all XRF results from this sampler were within 20% of the corresponding ICP values. As in previous studies, the best results were obtained with the GSP sampler using the average of three readings, with all XRF results within 20% of the corresponding ICP values and a slope close to 1 (0.99). Greater than 95% of XRF results were within 20% of the corresponding ICP values for the closed-face 37 mm cassette using the OSHA algorithm, and the IOM sampler using a sample area of 3.46 cm2. As in previous studies, considerable material was found on the interior walls of all samplers that possess an internal surface for deposition, at approximately the same proportion for all samplers. At the lead-acid battery recycler all five samplers in their optimal configurations gave good correlations (r2 > 0.92) between the two analytical methods over the entire range of found lead mass, which included the permissible exposure limit enforced in the USA by the Occupational Safety and Health Administration (OSHA). Linear regression on the results from most samplers gave almost 1 ratio 1 correlations (except for the Button sampler), indicating an absence of matrix effects from the presence of the smaller quantities of the other metals in the samples. A negative bias was found for the slope of the button sampler regression, in line with other studies. Even though very high concentrations of lead were encountered (up to almost 6 mg m(-3)) no saturation of the detector was observed. Most samplers performed well, with >90% of XRF results within +/- 25% of the corresponding ICP results for the optimum configurations. The OSHA algorithm for the CFC worked best without including the back-up pad with the filter.     

An observational case study of ozone and precursors inflow to South East England during an anticyclone

Summertime photochemical air pollution episodes within the United Kingdom have been proposed via modelling studies to be strongly influenced by regional scale inflow of air from the continental European boundary layer. We present a vertically resolved case study using measurements made from the NERC/Met Office BAe 146 research aircraft on 18th August 2005 over the South East of England and the North Sea during a weak anticyclone centred over Northern Europe. The vertical distribution of ozone, CO, NO(x), peroxyacetyl nitrate (PAN) and a wide range of both nonmethane hydrocarbons (NMHC) and oxygenated volatile organic compounds (OVOCs) were determined between 500 ft (approximately 152 m) and 7000 ft (approximately 2134 m) over the East Anglia coastline and 50 km inland. In excess of 80 ppbV ozone was observed within inflowing boundary layer air over the North Sea coast in a broad N-S sloping feature around 60 km wide. The inflowing feature of European origin was also observed further inland within the boundary layer albeit with lower, more variable, ozone mixing ratios. The increased variability in ozone over land was a product of titration by fresh surface emissions of NO via rapid upward transport in thermals, a hypothesis supported by the observed vertical wind speed component. Fast boundary layer mixing over land was further illustrated by a uniform distribution in reactive alkenes. A comparison between aircraft and surface O(3) UK AUN (Automatic Urban Network) measurements showed good agreement with the inland site, Sibton, but marked differences with the coastal monitoring site at Weybourne, potentially due to gradients established by ocean deposition in stably stratified marine air.     

Stratigraphic flux—A method for determining preferential pathways for complex sites

Experience with groundwater remediation over several decades has demonstrated that successful outcomes depend on quantitative conceptual site models (CSMs). Over the last 30 years, we have progressed from groundwater pump‐and‐treat remedies, which were largely designed based on a water supply perspective, to in situ and combined remedy strategies, which are only beginning to benefit from understanding the aquifer architecture and distribution of contaminant mass to assess plume maturity, mass flux, and more reliable means of fate and transport assessment. The U.S. Air Force funded the development of the Stratigraphic Flux approach to provide a framework for understanding contaminant transport pathways at its complex sites and enable more reliable and cost‐effective remediation. Stratigraphic Flux enables the development of quantitative, flux‐based CSMs that are founded in sequence stratigraphy, and high‐resolution hydraulic conductivity and contaminant distribution measurements. The result is a three‐dimensional graphical mapping of relative contaminant flux and classification of transport potential that is easy for all stakeholders to understand. The Stratigraphic Flux graphical model is based on a hydrofacies classification system that describes transport potential in three segments of the aquifer: transport zones—where the majority of groundwater flow occurs and transport rates are measured in feet per day; slow advection zones—where transport rates are measured in feet per year; and storage zones—where typically less than 1% of flow occurs, and diffusion dominates contaminant transport. The hydrofacies architectures are based on stratigraphy and transport potential is defined by grouping facies by orders of magnitude classes in hydraulic conductivity. By combining the hydrofacies architecture with contaminant concentration distributions, one can map relative contaminant flux to define and target the complex pathways that control contaminant transport and cleanup behavior. In this article, we describe the Stratigraphic Flux framework, focusing on the key information needed and the methods of analysis. We illustrate the results of its application to evaluate migration pathways for trichlorethylene and chromium at a former chrome pit at Air Force Plant 4 in Fort Worth, Texas. A comprehensive guidance document that describes the approach with a broad spectrum of tools and several site examples can be requested from the authors.     

The impacts of knowledge of the past on preferences for future landscape change

In this paper, we investigate whether people's knowledge of the past influences their preferences and values towards future landscape change. "Knowledge of the past" is one aspect of the information set held by individuals, and a well-established finding in economics is that changes in information can change preferences and values. The particular aspects of knowledge of the past we work with here are: (i) awareness of past landuse, as represented by woodland cover and (ii) awareness of differing and sometimes contradictory literary impressions of this past landscape. The case studies used here relate to prospective changes in woodland cover in two UK national parks, the Lake District and the Trossachs. We find that people who are made aware that the landscape has changed over time, or that perceptions of the landscape have changed over time, are more likely to favour changes to the current landscape (are less likely to favour the status quo). Knowledge of the past therefore seems to have an impact on preferences for future landscapes. We also investigate the impacts on preferences of how "special", how "wild" and how "worked in" people perceive the landscapes of these two national parks to be.     

Critical Sampling Points Methodology: Case Studies of Geographically Diverse Watersheds

Only with a properly designed water quality monitoring network can data be collected that can lead to accurate information extraction. One of the main components of water quality monitoring network design is the allocation of sampling locations. For this purpose, a design methodology, called critical sampling points (CSP), has been developed for the determination of the critical sampling locations in small, rural watersheds with regard to total phosphorus (TP) load pollution. It considers hydrologic, topographic, soil, vegetative, and land use factors. The objective of the monitoring network design in this methodology is to identify the stream locations which receive the greatest TP loads from the upstream portions of a watershed. The CSP methodology has been translated into a model, called water quality monitoring station analysis (WQMSA), which integrates a geographic information system (GIS) for the handling of the spatial aspect of the data, a hydrologic/water quality simulation model for TP load estimation, and fuzzy logic for improved input data representation. In addition, the methodology was purposely designed to be useful in diverse rural watersheds, independent of geographic location. Three watershed case studies in Pennsylvania, Amazonian Ecuador, and central Chile were examined. Each case study offered a different degree of data availability. It was demonstrated that the developed methodology could be successfully used in all three case studies. The case studies suggest that the CSP methodology, in form of the WQMSA model, has potential in applications world-wide.     

Dilution-based emissions sampling from stationary sources: Part 1--Compact sampler methodology and performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.     

Veterinary waste disposal: practice and policy in Durban, South Africa (2001-2003)

In South Africa, until recently, veterinary waste has not been included in definitions of health care waste, and so has been neglected as a contributor to the hazardous waste stream. Despite the application of, for example, the "Polluter Pays" principle in South African environmental legislation, to generators of waste, which would include veterinarians, there appears to be little awareness of and even less enforcement of the legislation in this regard. This paper reports on a 2001-2003 survey of management practices of the five waste contractors servicing just over half of the veterinarians in Durban, South Africa's second largest city. Some of their activities, when evaluated in terms of the legislation, guidelines and policies relating to waste handling and disposal, were found to be non-compliant. Since any discussion on waste management should take cognisance of waste from generation to final disposal, the responsibility of veterinarians as waste generators is also discussed in the light of the recent developments in health care waste management in South Africa. This study presents a review of past and current policies, legislation and guidelines that have application to veterinary waste. This is the first study to address veterinary waste disposal in any South African city.     

Preliminary results of modeled ozone uptake for Fagus sylvatica L. trees at selected EU/UN-ECE intensive monitoring plots

The objective of this study was to establish whether EU and UN-ECE/ICP-Forests monitoring data (i) provide the variables necessary to apply the flux-based modeling methods and (ii) meet the quality criteria necessary to apply the flux-based critical level concept. Application of this model has been possible using environmental data collected from the EU and UN-ECE/ICP-Forests monitoring network in Switzerland and Italy for 2000-2002. The test for data completeness and plausibility resulted in 6 out of a possible total of 20 Fagus sylvatica L. plots being identified as suitable from Switzerland, Italy, Spain, and France. The results show that the collected data allow the identification of different spatial and temporal areas and periods as having higher risk to ozone than those identified using the AOT40 approach. However, it was also apparent that the quality and completeness of the available data may severely limit a complete risk assessment across Europe.     

How environment and vole behaviour may impact rodenticide bromadiolone persistence in wheat baits after field controls of Arvicola terrestris?

We aimed to evaluate whether environmental factors affect the persistence of bromadiolone in baits in field treatment. Baits were distributed in three soils according to two types of distribution: (1) artificial galleries conform to agricultural practices; (2) storage cavities to mimic bait storage by voles. Persistence was evaluated for 30 days in galleries and 80 days in storage cavities in autumn and spring. The decrease of bromadiolone concentrations was described by a first-order kinetic model. In galleries, the half-lives ranged from 3.0 to 5.1 days in autumn and from 5.4 to 6.2 days in spring. The half-lives were similar between soils and seasons but the pattern of persistence differed lightly for two soils between seasons. Half-lives in storage cavities, 42.7 and 24.6 days in autumn and spring respectively, were longer than in galleries. To conclude, both soil characteristics and climatic conditions weakly influence persistence, while bait storage lengthens it dramatically.