Passive sampler derived air concentrations of PBDEs along an urban-rural transect: spatial and temporal trends

Passive air samplers consisting of polyurethane foam (PUF) disks housed in chambers were deployed at several sites along a approximately 75 km urban-rural gradient in Toronto and analyzed for polybrominated diphenyl ethers (PBDEs). Samplers were allowed to integrate gas-phase PBDEs over three consecutive seasons starting in the summer of 2000. PBDEs were fairly uniform along the transect with air concentrations in Toronto (10-30 pgm(-3)) about a factor of two greater than at rural sites. Lowest concentrations were observed during the winter and probably associated with reduced inputs from indoor sources of PBDEs and to a preference for PBDEs to partition to the particle-phase at colder temperatures. The composition of PBDEs in the air samples did not differ across the transect or for the different seasons.     

A hybrid method for inverse characterization of subsurface contaminant flux

The methods presented in this work provide a potential tool for characterizing contaminant source zones in terms of mass flux. The problem was conceptualized by considering contaminant transport through a vertical "flux plane" located between a source zone and a downgradient region where contaminant concentrations were measured. The goal was to develop a robust method capable of providing a statement of the magnitude and uncertainty associated with estimated contaminant mass flux values. In order to estimate the magnitude and transverse spatial distribution of mass flux through a plane, the problem was considered in an optimization framework. Two numerical optimization techniques were applied, simulated annealing (SA) and minimum relative entropy (MRE). The capabilities of the flux plane model and the numerical solution techniques were evaluated using data from a numerically generated test problem and a nonreactive tracer experiment performed in a three-dimensional aquifer model. Results demonstrate that SA is more robust and converges more quickly than MRE. However, SA is not capable of providing an estimate of the uncertainty associated with the simulated flux values. In contrast, MRE is not as robust as SA, but once in the neighborhood of the optimal solution, it is quite effective as a tool for inferring mass flux probability density functions, expected flux values, and confidence limits. A hybrid (SA-MRE) solution technique was developed in order to take advantage of the robust solution capabilities of SA and the uncertainty estimation capabilities of MRE. The coupled technique provided probability density functions and confidence intervals that would not have been available from an independent SA algorithm and they were obtained more efficiently than if provided by an independent MRE algorithm.     

Ambient Air Benzene Concentrations in Canada (1989-1993): Seasonal and Day of Week Variations,Trends, and Source Influences

Abstract

Since 1987, the Pollution Measurement Division of the Environmental Protection Service, Environment Canada, has operated a field program for measuring benzene in ambient air. With the cooperation of provincial and municipal environmental agencies, samples have been collected at over 30 urban and rural monitoring sites across the country. Samples are collected in evacuated canisters and analyzed by gas chromatography with a mass-selective detector. Using data from all sites, the composite average benzene concentration for Canada over the years 1989 to 1993 was 3.6 μg/m³ and the composite median was found to be 2.6 μ/m³. Benzene concentrations are highest at urban sites near major streets and at sites influenced by industrial sources. For eighteen urban and suburban trend sites (those with no nearby industrial sources), composite annual median benzene concentrations decreased by 20% between 1989 and 1993. For the same period, median benzene concentrations decreased by 33% at four trend sites with nearby industries. At most monitoring sites the parameters for benzene and CO are highly correlated; supporting the inventory estimate that most emissions of benzene are due to vehicle exhaust. For sites with nearby industrial sources of benzene, the industries are estimated to account for 35 to 70% of the benzene dose experienced at the sites. These site specific contributions are much more significant than the estimated national emissions assigned to industrial sources.     

Recent advances in mercury speciation analysis with focus on spectrometric methods and enriched stable isotope applications

This paper discusses some recent advances in spectrometric methods and approaches for mercury speciation analysis of environmental samples with focus on isotope dilution techniques for determination of mercury species' concentrations in gaseous samples and reaction rates in soils and sediments. Such analytical data is important inter alia in fundamental research on mercury biogeochemistry and for risk assessments of mercury-contaminated soils and sediments and for designing effective remedial actions. The paper describes how the use of enriched stable isotope tracers in mercury speciation analysis can improve the traceability and accuracy of results, facilitate rational method developments, and be useful for studying biogeochemical processes, i.e. rate of reactions and fluxes, of mercury species. In particular the possibilities to study and correct for unwanted species transformation reactions during sample treatment and to study "natural" transformations of species in environmental samples, or micro- and mesocosm ecosystems, during incubations are highlighted. Important considerations to generate relevant data in isotope tracer experiments as well as reliability and quality assurance of mercury speciation analysis in general are also discussed.     

Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

A comparison of mesh-adaptive LES with wind tunnel data for flow past buildings: Mean flows and velocity fluctuations

In this paper we address two important aspects of micro-scale urban airflow model evaluation: (a) the identification of key flow features as dictated by the physics of the problem and as captured by the simulations, and (b) the comparison of important model output parameters (mean flows and fluctuations) with experimental data. A series of mesh-adaptive large eddy simulations (LES) was carried out for the study of air flows within two intersecting street canyons with varying building configurations. The novelty of the approach lies in the combination of LES with mesh adaptivity, which allows a variable-filter length and the implementation of an anisotropic eddy-viscosity model. Both coarse and fine-mesh simulations were carried out, using single and parallel-processor systems respectively. The simulations showed clearly that the expected flow patterns such as the street canyon recirculation and the street-mouth vortices, as well as the exchange of air flow at the street intersections, can readily be captured by the mesh-adaptive LES.In addition, the detailed comparisons of mean flows and fluctuations of the resolved velocity field with the measured data showed that the simulation results agreed well with the patterns and trends of the wind tunnel measurements. In most cases the finer-mesh simulations improved considerably the accuracy of the mean flows, especially for the symmetrical configuration. The improvement in the predicted fluctuations was less obvious, with several detector locations underpredicting the measured values, although the overall comparison was also satisfactory. The typical errors for the mean flows for all three building configurations were less than 30%, whilst for the velocity fluctuations less that 40%. Both the simulated means flows and turbulence levels were generally more accurate in the streets parallel to the wind (streamwise direction) than in the streets normal to the wind.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

Ammonia emissions from different pig production scales and their temporal variations in the North China Plain

ABSTRACT

Pig production systems in China are shifting from small to industrial scale. Significant variation in housing ammonia (NH₃) emissions can exist due to differences in diet, housing design, and management practices. However, there is a knowledge gap regarding the impacts of farm-scale in China, which may be critical in identifying hotspots and mitigation targets. Here, continuous in-situ NH₃ concentration measurements were made at pig farms of different scales for sows and fattening pigs over periods of 3–6 days during two different seasons (summer vs. winter). For the sow farms, NH₃ emission rates were greater at the small farm (summer: 0.52 g pig^?1 hr^?1; winter: 0.21 g pig^?1 hr^?1) than at the large farm (summer: 0.34 g pig^?1 hr^?1; winter: 0.12 g pig^?1 hr^?1). For the fattening pig farms, NH₃ emission rates were greater at the large farm (summer: 0.22 g pig^?1 hr^?1; winter: 0.16 g pig^?1 hr^?1) than at the small farm (summer: 0.19 g pig^?1 hr^?1; winter: 0.07 g pig^?1 hr^?1). Regardless of farm scale, the NH₃ emission rates measured in summer were greater than those in winter; the NH₃ emission rates were greater in the daytime than at the nighttime; a positive relationship (R² = 0.06–0.68) was established between temperature and NH₃ emission rate, whereas a negative relationship (R² = 0.10–0.47) was found between relative humidity and NH₃ emission rate. The effect of farm-scale on indoor NH₃ concentration could mostly be explained by the differences in ventilation rates between farms. The diurnal variation in NH₃ concentration could be partly explained by ventilation rate (R² = 0.48–0.78) in the small traditional farms and by emission rate (R² = 0.26–0.85) in the large industrial farms, except for the large fattening pig farm in summer. Overall, mitigation of NH₃ emissions from sow farms should be a top priority in the North China Plain.

Implications: The present study firstly examined the farm-scale effect of ammonia emissions in the North China Plain. Of all farms, the sow farm was identified as the greatest source of ammonia emission. Regardless of farm scale, ammonia emission rates were observed to be higher in summer. Ammonia concentrations were mostly higher in the large industrial farms partly due to lower ventilation rates than in the small traditional farms.     

Relationships between metal concentrations in great tit nestlings and their environment and food

Metal concentrations (Ag, As, Cd, Cu, Hg, Ni, Pb, Zn) were determined in the feathers and excreta of nestling great tits (Parus major), in their main invertebrate prey (Lepidoptera larvae) and in vegetation samples, all collected from four sites along a pollution gradient. Metal contamination in vegetation samples increased significantly towards the pollution source. The Ag, As, Hg, Ni and Pb concentrations in food samples were significantly higher at the site closest to the pollution source compared to the other three sites. Great tit nestlings from the site closest to the pollution source had significantly higher concentrations of Ag, As, Hg and Pb in their excreta than did nestlings at the other three sites. For five metals (Ag, As, Cu, Ni and Pb), we found concentrations in caterpillars to be significantly positively correlated with vegetation samples. We also found clear significant positive correlations between excreta and caterpillars for Ag, As, Hg and Pb and between feathers and caterpillars for As and Pb. Our data suggest that excreta are a good monitor for the presence and concentrations of non-essential metals in the food and the environment of passerine birds.