Atmospheric deposition of fluoride in the lower Tamar Valley,Tasmania

Soluble fluoride (F⁻), measured using an ion-selective electrode, was monitored during 1982–1983 in monthly bulk (wet and dry) atmospheric deposition samples collected at 17 locations in the lower Tamar Valley, Tasmania, where an aluminium (Al) smelter is located. Glass samplers (funnel-bottle type) were used, with duplications by plastic samplers at five locations later. The spatial and temporal variations in F⁻ deposition in relation to wind flow and rainfall are discussed, and its impact on the environment is highlighted. The mean deposition rates of F⁻, as measured from September 1982 to August 1983, ranged from about 90 μg m⁻² day⁻¹ at the intended ‘background’ location to 12,568 μg m⁻²day⁻¹ at a location about 1 km east-southeast from the smelter. The depositional fluxes of F⁻ and insoluble Al (another elemental tracer of the smelter) are significantly correlated (P < 0.001). They were much higher within 3 km of the smelter, where vegetation damage by fluoride contamination was most evident. However, air emissions from the smelter could travel at least 10 km up the valley. Wet deposition was the predominant removal process for F⁻ during autumn and winter, while dry deposition appeared to be more significant in summer. The plastic samplers collected about 8 and 17% more F⁻ and Al, respectively, but with higher standard deviations. Thus the variations observed could be largely due to sampling fluctuations.     

Atmospheric deposition, retention, and stream export of dioxins and PCBs in a pristine boreal catchment

The mass-balance between diffuse atmospheric deposition of organic pollutants, amount of pollutants retained by the terrestrial environment, and levels of pollutants released to surface stream waters was studied in a pristine northern boreal catchment. This was done by comparing the input of atmospheric deposition of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and PCBs with the amounts exported to surface waters. Two types of deposition samplers were used, equipped with a glass fibre thimble and an Amberlite sampler respectively. The measured fluxes showed clear seasonality, with most of the input and export occurring during winter and spring flood, respectively. The mass balance calculations indicates that the boreal landscape is an effective sink for PCDD/Fs and PCBs, as 96.0-99.9 % of received bulk deposition was retained, suggesting that organic pollutants will continue to impact stream water in the region for an extended period of time.     

Practical considerations for addressing uncertainties in monitoring bulk deposition

The assessment of the deposition of both wet (rain and cloud) and dry sedimenting particles is a prerequisite for estimating element fluxes in ecosystem research. Many nations and institutions operate deposition networks using different types of sampler. However, these samplers have rarely been characterized with respect to their sink properties. Major errors in assessing bulk deposition can result from poor sampling properties and defective sampling strategies. Relevant properties are: sampler geometry and material, in particular the shape of the rim; sink properties for gases and aerosols; and microbial transformations of the collected samples. An adequate number of replicates allows the identification of samples which are contaminated, in particular by bird droppings. The paper discusses physical and chemical properties of the samplers themselves. The dependence of measurement accuracy on the number of replicates and the sampling area exposed is discussed. Recommendations are given for sampling strategies, and for making corrections and substitution of missing data.     

Field evaluation of two diffusive samplers and two adsorbent media to determine 1,3-butadiene and benzene levels in air

Two types of diffusive samplers, both of which are compatible with thermal desorption, but differ in their geometry—SKC-Ultra (badge-type) and Radiello (radial symmetry-type)—were evaluated indoors and outdoors under varying temperature, humidity and wind speed conditions, using the graphitized adsorbents Carbopack X or Carbograph 5 to measure 1,3-butadiene and benzene in ambient air. The results obtained by diffusive sampling were compared with results obtained using a conventional active sampling method over both long (1 week) and shorter periods (6–24 h). Analysis and detection were performed using an automatic thermal desorber (ATD) connected to a gas chromatograph-flame ionization detector (GC/FID). Results from each sampler and adsorbent combination were examined using ordinary or multiple linear regression analysis. The overall uncertainty (OU) was also determined. In general, the results obtained with both samplers showed good agreement with those obtained by active sampling. Carbopack X appeared to be a more efficient adsorbent than Carbograph 5 for 1,3-butadiene, but the two adsorbents were equivalent for benzene. No effects of either humidity or air velocity were observed. Minor temperature effects were observed for both samplers for 1,3-butadiene. In summary, the results confirmed the accuracy of sampling rates previously determined for the two samplers and adsorbents. We consider the two samplers to be suitable for stationary and personal monitoring for the general population of 1,3-butadiene and benzene in various environments, indoors and outdoors. They are almost independent of meteorological conditions and may be suitable for monitoring industrial atmospheres.     

Intercalibration of a passive wind-vane flux sampler against a continuous-flow denuder for the measurements of atmospheric ammonia concentrations and surface exchange fluxes

A passive wind-vane flux sampler is a simple low-cost device used to estimate long-term vertical fluxes of ammonia in the atmospheric surface boundary layer. The passive flux sampler measures the horizontal flux of ammonia. A vertical gradient of the horizontal flux, combined with micro-meteorological measurements of wind speed and temperature, is used to estimated the vertical flux of ammonia using a modified aerodynamic gradient technique. The passive wind-vane flux sampler gradient was calibrated against a gradient measured with fast response (6 min) continuous-flow denuders. The measurements were carried out at a heathland located in an intensive farming area in the centre of the Netherlands. A field campaign took place over 70 day period in the summer of 1996, during which the sampling periods of the passive wind-vane flux sampler varied between 3 and 9 days. The comparison clearly showed that the long-term measurements with the passive wind-vane flux samplers gave accurate average ammonia deposition values for the field campaign as a whole which deviated by only 18% from the reference flux. However, there was no significant correlation between the fluxes from the passive samplers and the reference method for the individual 10 periods which were compared. Possible explanations found for the lacking correlation were (I) a high percentage number of half-hour emission events within each period resulted in a significant large relative deviation between the fluxes, and (II) uncertainties in the reference method might also explain the lacking correlation. The passive wind-vane flux samplers proved to be a stable method for long-term measurements (months to years) due to a close to 100% optimal functioning during the field campaign.     

Validation of a flow-through sampler for pesticides and polybrominated diphenyl ethers in air

At locations without access to the electrical grid, a flow-through sampler (FTS) collects large volumes of air for the analysis of semi-volatile organic compounds (SVOCs). To test its performance under field conditions, an FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were co-deployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Polybrominated diphenyl ethers (PBDEs) and various pesticides were quantified in the samples taken by both samplers to test the FTS's applicability to relatively non-volatile and slightly polar SVOCs. Air concentrations in samples taken with the FTS over five 2-week periods compare favourably with the average of the concentrations in several 24-h active high volume samples taken during the same period. In particular, time trends, temperature dependence relationships, and isomer ratios show a reasonable agreement between the two sampling techniques. An empirical linear solvation energy relationship for predicting the apparent theoretical plate number of the PUF assembly used in the FTS illustrates the effect of chemical properties, as well as temperature and wind speed, on sampling efficiency. In the absence of electrical power, the FTS can collect SVOCs from large air volumes as reliably and quantitatively as traditional HiVol samplers, although without separating gas and particle phase.     

Evaluation of high volume particle sampling and sample handling protocols for ambient urban air mutagenicity determinations.

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM10 Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22 degrees C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at -70 degrees C to -80 degrees C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set.(ABSTRACT TRUNCATED AT 250 WORDS)     

Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

Modelling atmospheric bulk deposition of Pb,Zn and Cd near a former Pb–Zn mine in West Greenland using transplanted Flavocetraria nivalis lichens

Atmospheric deposition of lead (Pb), zinc (Zn) and cadmium (Cd) was investigated near the former Black Angel Pb–Zn mine in Maarmorilik, West Greenland during 2010–2011. Thalli of the lichen Flavocetraria nivalis were transplanted from an uncontaminated site into sites near the mine and collected the following year. At 20 of the total 21 sites, concentrations of Pb, Zn and Cd were significantly elevated in lichens after 1 year of transplantation compared to initial concentrations. Elevated concentrations were observed within a distance of approx. 20 km from the mining area. Concentrations decreased with increasing distance from the mine and the relation was well described using a power function with a negative exponent (r² = 0.90; 0.83 and 0.83 for Pb; Zn and Cd). To examine the relation between metal concentrations/uptake in lichen transplants and atmospheric bulk deposition, 10 Bergerhoff dust samplers were placed near lichen transplants and samplers and lichens were collected after a 7-weeks exposure period. A significant linear correlation was observed between metal concentrations in lichen transplants and atmospheric bulk metal deposition (r² = 0.94; 0.88 and 0.89 for Pb; Zn and Cd). Combining the results and including an area distribution within a defined metal deposition area, the “annual” deposition of Pb, Zn and Cd as dust was estimated during the 2010–2011 snow-free period (～5 months). The results reveal that 20 years after mine closure, 770 kg Pb, 3700 kg Zn and 24 kg Cd were still being deposited as dust per year (snow-free period only) within a distance of 20 km from the mine.     

A passive flux denuder for evaluating emissions of ammonia at a dairy farm

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH3), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling has required active sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH3 from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH3 flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH3 flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH3 emissions.     

A Passive Flux Denuder for Evaluating Emissions of Ammonia at a Dairy Farm

Abstract

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH₃), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH₃ from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH₃ flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH₃ flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH₃ emissions.     

Planning A State-Wide Air Pollution Advisory Service

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM₁₀ Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon® impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22°C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at ?70°C to ?80°C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set. Results indicate that the sample handling variations and collection period variables had no significant effect on recovery of organics or mutagens. However, a filter type difference was observed. The sonication extraction of organics and mutagens was significantly greater for TIGF filters than for glass fiber or quartz. Results from a second phase of study indicated differences in extracted organics and mutagens for these filter types.     

The use of vegetation,bees, and snails as important tools for the biomonitoring of atmospheric pollution—a review

The continuous discharge of diverse chemical products in the environment is nowadays of great concern to the whole world as some of them persist in the environment leading to serious diseases. Several sampling techniques have been used for the characterization of this chemical pollution, although biomonitoring using natural samplers has recently become the technique of choice in this field due to its efficiency, specificity, and low cost. In fact, several living organisms known as biomonitors could accumulate the well-known persistent environmental pollutants allowing their monitoring in the environment. In this work, a review on environmental biomonitoring is presented. The main sampling techniques used for monitoring environmental pollutants are first reported, followed by an overview on well-known natural species used as passive samplers and known as biomonitors. These species include conifer needles, lichen, mosses, bees and their byproducts, and snails, and were widely used in recent research as reliable monitors for environmental pollution.

     

Mobile passive samplers: concept for a novel mode of exposure

Integrative passive sampling with devices such as semipermeable membrane devices generally relies on rigs for month-long static exposures in water. We evaluate here whether mobile exposures of passive samplers can provide reliable estimates of dissolved contaminant concentrations. Mobile exposures were obtained by towing samplers fastened to the end of a benthic trawl net. Significant and reproducible absorption of polycyclic aromatic hydrocarbons during 5 h-long deployments was made possible by high sampling rates resulting from high water turbulences during towing at 1.2-1.5 knots. Sampling rates (72-215 L d⁻¹) estimated from the dissipation of performance reference compounds were supported by in situ calibration with samplers exposed for a 30 days in the vicinity of the test site. Higher fluoranthene and pyrene absorption in samplers exposed to the trawling-induced sediment plume could be attributed to desorption from re-suspended sediments. This mode of exposure has the potential to be used in monitoring programmes.     

Active moss biomonitoring of trace elements with Sphagnum girgensohnii moss bags in relation to atmospheric bulk deposition in Belgrade, Serbia

Active biomonitoring with wet and dry moss bags was used to examine trace element atmospheric deposition in the urban area of Belgrade. The element accumulation capability of Sphagnum girgensohnii Russow was tested in relation to atmospheric bulk deposition. Moss bags were mounted for five 3-month periods (July 2005-October 2006) at three representative urban sites. For the same period monthly bulk atmospheric deposition samples were collected. The concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, and Pb were determined by instrumental neutron activation analyses and atomic absorption spectrometry. Significant accumulation of most elements occurred in the exposed moss bags compared with the initial moss content. High correlations between the elements in moss and bulk deposits were found for V, Cu, As, and Ni. The enrichment factors of the elements for both types of monitor followed the same pattern at the corresponding sites.     

New passive samplers for chlorinated semivolatile organic pollutants in ambient air

Two new types of passive samplers were designed and tested on semivolatile organic compounds. The first type (a spiral-rod sampler) consists of a low-density polyethylene membrane acting as a permeation film and a silicone elastomer as the receiving material; the second (a stir-bar sampler) has the same membrane material but a polydimethylsiloxane-coated stir bar acting as the collector phase and installed radially symmetrically in the sampler. The advantages of the new samplers are their simple design, low costs, and their easy processing via thermodesorption coupled with capillary gas chromatography and mass selective detection. In both samplers, the uptake of selected analytes was integrative over exposure periods of up to 384 h. The sampling rates calculated from a laboratory calibration study using the chlorinated semivolatiles hexachlorobenzene, hexachlorocyclohexane isomers and polychlorinated biphenyls ranged from 88.1 ml h-1 for delta-hexachlorocyclohexane to 3443 ml h-1 for 2,2',5,5'-tetrachlorobiphenyl. A field trial at a hazardous waste dump near Bitterfeld, Germany, for up to 21 days combined with periodical determinations of air concentrations using low-volume sampling indicated that the new samplers can in principle be used in the field, although the sampling rates derived from the field results differed considerably from the laboratory findings. Nevertheless the preliminary results suggest that the new sampler types are promising for the long-term air monitoring of semivolatiles.     

Particle deposition in low-speed,high-turbulence flows

The experimental and numerical study considers the concentration of airborne particulate contaminants, such as spores of spoilage fungi, and their deposition on a surface, in a Petri dish, and on a warm box-shaped product placed in a food-processing environment. Field measurements by standard, active and passive samplers provide typical values of airborne concentrations and specific deposition fluxes. Velocity and turbulence data from field studies are used as input in large eddy simulations of the process, and estimates of deposition fluxes are of the same order of magnitude as those deduced from field measurements. Particle deposition is shown to be associated with near-wall coherent structures. Flow reversal, simulated by impulsive start, is shown to give higher deposition rates than steady mean flows.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Long-term atmospheric bulk deposition of polycyclic aromatic hydrocarbons (PAHs) in rural areas of Southern Germany

A novel passive sampling technique using a funnel–adsorber–cartridge device was adopted and validated in the field during a long-term monitoring program on the atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in three rural regions of southern Germany. Apart from seasonal variations, fairly stable annual deposition rates around 200 μg m⁻² yr⁻¹ for the sum of PAHs were obtained. The time-integrating passive samplers showed that spatial variability due to topography was negligible and differences between open-field and forest deposition were within a factor of 2. Based on correlations with ambient temperature, advection was identified as the most important factor that controls the atmospheric deposition of PAHs. Gas-adsorption contributes significantly to the deposition of the semivolatile compounds in forests, but particle deposition seems to be the major pathway for all PAHs.     

Duplicate sampling reproducibility of atmospheric residues of herbicides for paired pan and high-volume air samplers

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.