A comparison of X-ray fluorescence and wet chemical analysis of air filter samples from a scrap lead smelting operation

Personal and area air samples were taken at a scrap lead smelter operation in a bullet manufacturing facility. Samples were taken using the 37-mm styrene-acrylonitrile closed-face filter cassette (CFC, the current US standard device for lead sampling), the 37-mm GSP or "cone" sampler, the 25-mm Institute of Occupational Medicine (IOM) inhalable sampler, and the 25-mm Button sampler (developed at the University of Cincinnati). Polyvinylchloride filters were used for sampling. The filters were pre- and post-weighed, and analyzed for lead content using a field-portable X-ray fluorescence (XRF) analyzer. The filters were then extracted with dilute nitric acid in an ultrasonic extraction bath and the solutions were analyzed by inductively coupled plasma optical emission spectroscopy. 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. The single reading from the 25-mm filters was adjusted for the nominal area of the filter to obtain the mass loading, while the three readings from the 37-mm filters were inserted into two different algorithms for calculating the mass loadings, and the algorithms were compared. The IOM sampler was designed for material collected in the body of the sampler to be part of the collected sample as well as that on the filter. Therefore, the IOM sampler cassettes were rinsed separately to determine if wall-loss corrections were necessary. All four samplers gave very good correlations between the two analytical methods above the limit of detection of the XRF procedure. The limit of detection for the 25-mm filters (5 microg) was lower than for the 37-mm filters (10 microg). The percentage of XRF results that were within 25% of the corresponding ICP results was evaluated. In addition, the bias from linear regression was estimated. Linear regression for the Button sampler and the IOM sampler using single readings and the GSP using all tested techniques for total filter loading gave acceptable XRF readings at loadings equivalent to sampling at the OSHA 8-hour Action Level and Permissible Exposure Limit. However, the CFC only had acceptable results when the center reading corrected for filter area was used, which was surprising, and may be a result of a limited data set. In addition to linear regression, simple estimation of bias indicated reasonable agreements between XRF and ICP results for single XRF readings on the Button sampler filters, (82% of the individual results within criterion), and on the IOM sampler filters (77% or 61%--see text), and on the GSP sampler filters using the OSHA algorithm (78%). As a result of this pilot project, all three samplers were considered suitable for inclusion in further field research studies.     

Biomonitoring in the Boulder River Watershed, Montana, USA: Metal Concentrations in Biofilm and Macroinvertebrates, and Relations with Macroinvertebrate Assemblage

Portions of the Boulder River watershed contain elevated concentrations of arsenic, cadmium, copper, lead, and zinc in water, sediment, and biota. We measured concentrations of As, Cd, Cu, Pb, and Zn in biofilm and macroinvertebrates, and assessed macroinvertebrate assemblage and aquatic habitat with the objective of monitoring planned remediation efforts. Concentrations of metals were generally higher in downstream sites compared with upstream or reference sites, and two sites contained metal concentrations in macroinvertebrates greater than values reported to reduce health and survival of resident trout. Macroinvertebrate assemblage was correlated with metal concentrations in biofilm and macroinvertebrates. However, macroinvertebrate metrics were significantly correlated with a greater number of biofilm metals (8) than metals in invertebrates (4). Lead concentrations in biofilm appeared to have the most significant impact on macroinvertebrate assemblage. Metal concentrations in macroinvertebrates were directly proportional to concentrations in biofilm, indicating biofilm as a potential surrogate for monitoring metal impacts in aquatic systems.     

A review of workplace aerosol sampling procedures and their relevance to the assessment of beryllium exposures

Standardized conventions governing the fractions of airborne particles that can penetrate the human head airways, the thoracic airways and the alveolar spaces have been internationally (although not universally) adopted. Several agencies involved in setting limit values for occupational exposure concentrations have taken these conventions into account when considering the appropriate standard for specific chemicals, in order to ensure the standards are biologically relevant. A convention is selected based on the characteristic health effects, and forms the basis of measurement against the limiting concentration value. In order to assess exposure for comparison to this metric or any other purposes, it is necessary to choose a sampler whose performance matches the convention, and protocols have been developed and used to test sampler performance. Several aerosol sampling devices are available, nominally at least, for each of the conventions. Some considerations important to the sampling of airborne particles containing beryllium with regard to the sampling conventions, the test protocols and sampler performance are discussed.     

Streamwater phosphorus and nitrogen across a gradient in rural–agricultural land use intensity

This paper provides an overview of the impacts of rural land use on lowland streamwater phosphorus (P) and nitrogen (N) concentrations and P loads and sources in lowland streams. Based on weekly water quality monitoring, the impacts of agriculture on streamwater P and N hydrochemistry were examined along a gradient of rural–agricultural land use, by monitoring three sets of ‘paired’ (near-adjacent) rural headwater streams, draining catchments which are representative of the major geology, soil types and rural/agricultural land use types of large areas of lowland Britain. The magnitude and timing of P and N inputs were assessed and the load apportionment model (LAM) was applied to quantify ‘continuous’ (point) source and ‘flow-dependent’ (diffuse) source contributions of P to these headwater streams. The results show that intensive arable farming had only a comparatively small impact on streamwater total phosphorus (TP loads), with highly consistent stream diffuse-source TP yields of ca. 0.5 kg-P ha^?1 year^?1 for the predominantly arable catchments with both clay and loam soils, compared with 0.4 kg-P ha^?1 year^?1 for low agricultural intensity grassland/woodland on similar soil types. In contrast, intensive livestock farming on heavy clay soils resulted in dramatically higher stream diffuse-source TP yields of 2 kg-P ha^?1 year^?1. The streamwater hydrochemistry of the livestock-dominated catchment was characterised by high concentrations of organic P, C and N fractions, associated with manure and slurry sources. Across the study sites, the impacts of human settlement were clearly identifiable with effluent inputs from septic tanks and sewage treatment works resulting in large-scale increases in soluble reactive phosphorus (SRP) loads and concentrations. At sites heavily impacted by rural settlements, SRP concentrations under baseflow conditions reached several hundred μg-P L^?1. Load apportionment modelling demonstrated significant ‘point-source’ P inputs to the streams even where there were no sewage treatment works within the upstream catchment. This indicates that, even in sparsely populated rural headwater catchments, small settlements and even isolated groups of houses are sufficient to cause significant nutrient pollution and that septic tank systems serving these rural communities are actually operating as multiple point sources, rather than a diffuse input.     

Two-phase jet releases,droplet dispersion and rainout,II. Rainout experiments

This paper describes the results of the first experimental stage of Phase IV of a Joint Industry Project (JIP) on liquid jets and two-phase droplet dispersion. The objective of this stage of the JIP was to generate experimental rainout data for non-flashing water and xylene experiments. See the overview companion paper I for a wider overview of the problem, model implementation and associated model validation.A range of orifice sizes (2.5 and 5 mm) and stagnation pressures (4–16 barg) were applied. Measurements included flow rate, initial droplet size, plume concentrations/temperatures for a range of downstream locations, and distributed rainout.Instead of the Phase Doppler Anemometry method used for droplet size measurements earlier in the JIP, a photographic technique was applied in an attempt to include measurement of the larger (non-spherical) droplets. This enabled a more accurate evaluation of the initial droplet size distribution and a much clearer understanding of the droplet morphology. The results showed that the droplet behaviour in the jet is more complex than had been anticipated with the mass distribution dominated by a very small number of large non-spherical droplets. Consequently a large number of spray images were required to evaluate an accurate size distribution.Distributed rainout was measured by weighing the amount of rainout in trays positioned along the jet direction. The rainout results showed a good degree of repeatability and internal consistency. They indicated that an increasing proportion of the released material did not rainout for increasing pressure. Rainout distance also increased with increasing pressure. Evaporation of the liquid was confirmed by temperature measurements, which showed the effect of evaporative cooling.Xylene concentration measurements (up to 1%) were carried out using a direct reading photoionization detector calibrated for xylene (measuring vapour only). For a limited dataset, the accuracy of these measurements was estimated by means of comparison against an alternative more time-consuming concentration method (xylene absorption onto a charcoal filter; measuring both vapour and liquid). The concentration measurements displayed several consistent qualitative features. For example, at a given downstream distance, the peak concentration increases with increasing pressure and nozzle diameter and the vertical height at which the peak is achieved increases. The cross-stream profiles displayed a consistent tendency to increased concentration at the edge of the jet, and the reason for this has not been established.Finally recommendations are provided for potential future work.     

Effect of fresh green waste and green waste compost on mineral nitrogen, nitrous oxide and carbon dioxide from a Vertisol

Incorporation of organic waste amendments to a horticultural soil, prior to expected risk periods, could immobilise mineral N, ultimately reducing nitrogen (N) losses as nitrous oxide (N₂O) and leaching. Two organic waste amendments were selected, a fresh green waste (FGW) and green waste compost (GWC) as they had suitable biochemical attributes to initiate N immobilisation into the microbial biomass and organic N forms. These characteristics include a high C:N ratio (FGW 44:1, GWC 35:1), low total N (<1%), and high lignin content (>14%). Both products were applied at 3 t C/ha to a high N (plus N fertiliser) or low N (no fertiliser addition) Vertisol soil in PVC columns. Cumulative N₂O production over the 28 day incubation from the control soil was 1.5 mg/N₂O/m², and 11 mg/N₂O/m² from the control + N. The N₂O emission decreased with GWC addition (P < 0.05) for the high N soil, reducing cumulative N₂O emissions by 38% by the conclusion of the incubation. Analysis of mineral N concentrations at 7, 14 and 28 days identified that both FGW and GWC induced microbial immobilisation of N in the first 7 days of incubation regardless of whether the soil environment was initially high or low in N; with the FGW immobilising up to 30% of available N. It is likely that the reduced mineral N due to N immobilisation led to a reduced substrate for N₂O production during the first week of the trial, when soil N₂O emissions peaked. An additional finding was that FGW + N did not decrease cumulative N₂O emissions compared to the control + N, potentially due to the fact that it stimulated microbial respiration resulting in anaerobic micro sites in the soil and ultimately N₂O production via denitrification. Therefore, both materials could be used as post harvest amendments in horticulture to minimise N loss through nitrate-N leaching in the risk periods between crop rotations. The mature GWC has potential to reduce N₂O, an important greenhouse gas.     

An approach for measuring methane emissions from whole farms

Estimates of enteric methane (CH4) emissions from ruminants are typically measured by confining animals in large chambers, using head hoods or masks, or by a ratiometric technique involving sampling respired air of the animal. These techniques are not appropriate to evaluate large-scale farm emissions and the variability between farms that may be partly attributed to different farm management. This study describes the application of an inverse-dispersion technique to calculate farm emissions in a controlled tracer-release experiment. Our study was conducted at a commercial dairy farm in southern Alberta, Canada (total of 321 cattle, including 152 lactating dairy cows). Sulfur hexafluoride (SF6) and CH4 were released from 10 outlet locations (barn and open pens) using mass-flow controllers. A Lagrangian stochastic (LS) dispersion model was then used to infer farm emissions from downwind gas concentrations. Concentrations of SF6 and CH4 were measured by gas chromatography analysis and open path lasers, respectively. Wind statistics were measured with a three-dimensional sonic anemometer. Comparing the inferred emissions with the known release rate showed we recovered 86% of the released CH4 and 100% of the released SF6. The location of the concentration observations downwind of the farm was critically important to the success of this technique.     

Sub-cooled and flashing liquid jets and droplet dispersion I. Overview and model implementation/validation

Many accidents involve two-phase releases of hazardous chemicals into the atmosphere. This paper describes the results of a third phase of a Joint Industry Project (JIP) on liquid jets and two-phase droplet dispersion. The aim of the project is to increase the understanding of the behaviour of sub-cooled non-flashing and superheated flashing liquid jets, and to improve the prediction of initial droplet size, droplet dispersion and rainout.Phase III of the JIP first included scaled experiments for materials with a range of volatilities (water, cyclohexane, butane, propane and gasoline). These experiments were carried out by Cardiff University including measurements of flow rate and initial droplet size across the full relevant range of superheats. See the companion paper II for further details of these experiments and the derivation of new refined correlations for droplet size distribution and Sauter Mean Diameter. Furthermore large-scale butane experiments were carried out by INERIS (France) to ensure that for more realistic scenarios the derived droplet size correlations are accurate.Model validation and model improvements were carried out by DNV Software, including validation of release rate and initial droplet size against the above scaled and large-scale experiments. New correlations for droplet size distribution and Sauter Mean Diameter (SMD) were implemented into the Phast discharge model. These were compared against a range of other droplet size and rainout correlations published in the literature, in conjunction with validation against an extensive set of experiments. It was shown that the new droplet size correlation agrees better against experimental data than the existing Phast correlation. To further improve the rainout prediction, the Phast dispersion model (UDM) was also extended to allow simultaneous modelling of a range of droplet sizes and distributed rainout (rather than rainout at one point).