Different collector types for sampling deposition of polycyclic aromatic hydrocarbons--comparison of measurement results and their uncertainty

Different collector types, sample workup procedures and analysis methods to measure the deposition of polycyclic aromatic hydrocarbons (PAH) were tested and compared. Whilst sample workup and analysis methods did not influence the results of PAH deposition measurements, using different collector types changed the measured deposition rates of PAH significantly. The results obtained with a funnel-bottle collector showed the highest deposition rates and a low measurement uncertainty. The deposition rates obtained with the wet-only collectors were the lowest at industrial sites and under dry weather conditions. For the open-jar collectors the measurement uncertainty was high. Only at an industrial site with extremely high PAH deposition rates the results of open-jar collectors were comparable to those obtained with funnel-bottle collectors. Thus, if bulk deposition of PAH has to be measured, funnel-bottle combinations are proved to be the collectors of choice. These collectors were the only ones always fulfilling the requirements of European legislation.     

Three-year monitoring results of nitrate and ammonium wet deposition in Thailand

Wet deposition is one of the important sources of nitrogen input into the ecosystem. It also contributes to rain acidity in some environments. In this study we reported the annual as well as seasonal trends of nitrogen wet deposition at three locations in Thailand: Bangkok, Chiang Mai and Nan. Comparison of nitrogen wet deposition between in rural and in the urban areas was also made. Daily rainfall was measured and monthly rainwater was collected for nitrogen analysis during 1999–2002. The average NO₃ ^– concentration in rainwater collected from the rural sites (60 km from urban area) was around 0.2–0.3 mg L^–1, while that from the urban areas of Chiang Mai and Nan cities it was 0.4–0.5 mg L^–1. NH₄ ⁺ concentration in rainwater showed the similar ranges to that of NO₃ ^– , except at Nan where concentration was not significantly different between the urban and rural sites. On the other hand, the average concentrations of NO₃ ^– were higher at Bangkok site than other sites, while concentration of NH₄ ⁺ was almost the same between Chiang Mai and Bangkok. Wet deposition of NO₃ ^– at the rural sites of Chiang Mai and Nan ranged from 2.1 to 3.2 kg N ha^–1 yr^–1, while at the urban sites this ranged from about 6 kg N ha^–1 yr^–1 in Chiang Mai and Nan Cities to 8.6 kg N ha^–1 yr^–1 in Bangkok. Wet deposition of NH₄ ⁺ at the rural sites of Chiang Mai and Nan was about 2.4 to 3.6 kg N ha^–1 yr^–1 and at the urban sites of Chiang Mai, Nan and Bangkok this was 7.7, 4.9 and 8.1 kg N ha^–1 yr^–1, respectively. Thus, it was concluded that wet deposition of both nitrogen species was significantly higher at the urban sites than at the rural sites.     

Precipitation composition and wet deposition temporal pattern in Central Serbia for the period from 1998 to 2004

Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate [Formula: see text], sulfate [Formula: see text], sodium (Na(+)), ammonium [Formula: see text], potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was [Formula: see text] with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of [Formula: see text] was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).     

Atmospheric wet deposition of soluble macro-nutrients in the Cilician Basin, north-eastern Mediterranean sea

In order to estimate wet deposition atmospheric fluxes of macro-nutrients into the eastern Mediterranean coastal waters, soluble inorganic phosphate (PO4(3-)), nitrate (NO3-) and nitrite (NO2-) concentrations in precipitation (from February 1996 to June 1997) have been measured at a coastal sampling site, Erdemli, Turkey. Water-soluble inorganic PO4(3)-P, a reactive, bioavailable, limiting macro-nutrient in the oligotrophic waters of the eastern Mediterranean was studied with respect to its contribution to biological productivity. Reactive PO4(3-)-P and NO2(-) + NO3(-)-N concentrations were found to be highly variable in rainwater samples. One of the aims of the study was to determine the contribution of dust transport to the soluble macro-nutrient budget of the eastern Mediterranean. No differences were found between the mean reactive P and NO(2-) + NO3(-)-N concentrations of "red rain" and normal rain events. Most likely as a result of low solubility of crustal phosphorus, dust episodes were not found to be important sources of reactive P, in terms of wet deposition. The annual wet deposition fluxes of reactive PO4(3-)-P and NO2(-) + NO3(-)-N into the Cilician Basin were respectively estimated to be 0.010 g P m(-2) per year and 0.23 g N m(-2) per year, which are comparable to the fluxes from land-based sources in the north-eastern Mediterranean. The incorporation of water soluble bioavailable PO4(3-)-P and NO2(-) + NO3(-)-N delivered via atmospheric wet deposition could be responsible for approximately 3.3% (0.40 g C m(-2) per year) and 11.0% (1.31 g C m(-2) per year) respectively, of the mean annual new production in the north-eastern Mediterranean.     

A simple method for the extraction of mutagens from airborne particles

Organic materials were extracted with acetone from filters of airborne particles by soaking, shaking, soxhletion, and sonication. These extracts were tested with and without S9 for mutagenicity using Ames assay and arabinose-resistant assay of Salmonella typhimurium. Among the extraction methods, soaking extract had the highest mutagenic activity followed by sonication, shaking, and soxhletion in both the assays. With the samples studied, it was concluded that soaking with acetone for 1/2 hr is the simplest and an efficient procedure for the extraction of mutagens from airborne particles.Results of cooperative investigation of NIOSH and West Virginia Agricultural and Forstry Experimental Station. Published with the approval of the Director of the West Virginia Agricultural and Forestry Experiment Station as Scientific Paper No. 1822.     

Spatial and temporal estimation of soil loss for the sustainable management of a wet semi-arid watershed cluster

The ungauged wet semi-arid watershed cluster, Seethagondi, lies in the Adilabad district of Telangana in India and is prone to severe erosion and water scarcity. The runoff and soil loss data at watershed, catchment, and field level are necessary for planning soil and water conservation interventions. In this study, an attempt was made to develop a spatial soil loss estimation model for Seethagondi cluster using RUSLE coupled with ARCGIS and was used to estimate the soil loss spatially and temporally. The daily rainfall data of Aphrodite for the period from 1951 to 2007 was used, and the annual rainfall varied from 508 to 1351 mm with a mean annual rainfall of 950 mm and a mean erosivity of 6789 MJ mm ha^?1 h^?1 year^?1. Considerable variation in land use land cover especially in crop land and fallow land was observed during normal and drought years, and corresponding variation in the erosivity, C factor, and soil loss was also noted. The mean value of C factor derived from NDVI for crop land was 0.42 and 0.22 in normal year and drought years, respectively. The topography is undulating and major portion of the cluster has slope less than 10°, and 85.3 % of the cluster has soil loss below 20 t ha^?1 year^?1. The soil loss from crop land varied from 2.9 to 3.6 t ha^?1 year^?1 in low rainfall years to 31.8 to 34.7 t ha^?1 year^?1 in high rainfall years with a mean annual soil loss of 12.2 t ha^?1 year^?1. The soil loss from crop land was higher in the month of August with an annual soil loss of 13.1 and 2.9 t ha^?1 year^?1 in normal and drought year, respectively. Based on the soil loss in a normal year, the interventions recommended for 85.3 % of area of the watershed includes agronomic measures such as contour cultivation, graded bunds, strip cropping, mixed cropping, crop rotations, mulching, summer plowing, vegetative bunds, agri-horticultural system, and management practices such as broad bed furrow, raised sunken beds, and harvesting available water using farm ponds and percolation tanks. This methodology can be adopted for estimating the soil loss from similar ungauged watersheds with deficient data and for planning suitable soil and water conservation interventions for the sustainable management of the watersheds.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.     

A field-based spectrophotometric flow-injection system for automatic determination of chloride in soil water

The use of chloride as a tracer for soil water investigations is discussed. Limitations with laboratory based soil core and field based sampling are considered with respect to the poor suitability of the data for rigorous assessment of mechanistic models. Investigation of water movement in soil has been restricted by limitations in spatial and temporal sampling. Fine resolution sampling generates large numbers of samples which cause problems with post sampling laboratory analysis. This paper describes a field-based system for the analysis of chloride in soil water. There are three component parts to the system, (i) a custom sampling sub-system comprising of ceramic cup suction samplers and sample traps, (ii) a sample routing sub-system to channel sample to (iii) a sample analysis sub-system utilizing a flow injection method for sample analysis using a custom built photo-diode detector. The three sub-systems were controlled by a suitably equipped personal computer. A calibration procedure is described with a third order polynomial equation derived to convert millivolt response from the detector into chloride concentration. Field and laboratory data from a tracer experiment are presented and discussed, and it is concluded that the system is well suited to field-based applications. Finally it is noted that the photo-detector is suitable for colourimetric analysis of any tracer with suitable chemical determination.     

Wipe sampling as a tool for monitoring aerosol deposition in workplaces

As a complement to traditional exposure assessment, monitoring deposition of aerosols can be a simple and quick screening method for identifying deposited aerosols. In this presentation examples of screening studies, based on wipe sampling in combination with adequate analytical techniques, are described. These screening methods are rapid, simple and easy to carry out. The examples given in this presentation show a broad applicability and the methods are proven useful for assessing aerosol distribution in the workplace as well as to identify target spots for more extensive assessment of a worker's exposure situation.     

Value functions for environmental pollutants: A technique for enhancing the assessment of expert judgements

This paper presents a new procedure to assess value functions for environmental pollutants. It has been particularly designed for eliciting expert-based value functions for pollutant substances. The main features of the model are the possibility to integrate direct and indirect assessment techniques, the possibility to make explicit assessment uncertainties and to avoid forcing quantitative judgements. The main aim of the procedure is to improve the reliability of the assessment but also to make the expert's task easier by using qualitative judgements more frequently. The procedure has been developed especially for soil pollutants, for which an application is described.     

A simple extraction procedure for determination of total mercury in crude oil

The determination of mercury in crude oil and petroleum products is particularly difficult due to the volatile nature of both mercury and the matrix, which may lead to significant loss of the analyte. A simple extraction method for total mercury has been developed to determine total mercury in crude oil using cold vapor atomic fluorescence spectrometry. The homogenized crude oil sample was diluted to 5, 10, and 20 % (w/w) in toluene. The diluted crude oil samples were spiked with 10 and 40 μg/kg (w/w). The samples were extracted using an oxidant/acid solution, BrCl/HCl. The mercury was extracted into the aqueous phase; the ionic mercury was then reduced to volatile elemental mercury (Hg⁰) by stannous chloride (SnCl₂). The mercury vapor was detected by Merlin cold vapor atomic fluorescence spectrometry at a 253.7-nm wavelength. The average recoveries for mercury in spiked diluted crude oil (10 and 40 μg/kg, w/w) were between 96 and 103 %, respectively, in 5 and 10 % spiked diluted crude oil. Whereas, low recoveries (<50 %) were recorded in 20 % diluted spiked crude oil. The method detection limit was calculated as t _{(0.01)(n ? 1)}?×?SD where t is the student's value for 99 % confidence level and standard deviation estimate with n???1 degrees of freedom. The method detection limit was found to be 0.38 μg/kg based on 5 g of diluted crude oil sample. The method is sensitive enough to determine low levels of mercury in crude oil.     

A comparison of X-ray fluorescence and wet chemical analysis for lead on air filters from different personal samplers used in a bronze foundry

Portable X-ray fluorescence (XRF) technology may provide faster turn-around without compromising accuracy when assessing personal exposures to metals such as lead, but it has only been tested in limited field environments. This study is part of a series, where different sampler types are used to collect airborne lead in different environments for presentation to a portable XRF analyzer. In this case personal samples were taken at a bronze foundry where lead is added to an alloy of copper, zinc and iron to improve casting, using the closed-face 37 mm cassette, 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. Following XRF analysis the samples were extracted with acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP). For lead, all five samplers gave correlations (r(2)) greater than 0.9 between the two analytical methods over the entire range of found lead mass, which encompassed both the action level and the permissible exposure limit enforced in the USA by the Occupational Safety and Health Administration (OSHA). However, a correction was required to adjust linear regression trendlines to give a 1 : 1 correlation for the average of three readings across the GSP sampler, and a similar correction was required for the single readings from the IOM sampler and the 25 mm filter cassette. The bias possibly is due to interference from other metals, possibly copper which can absorb the fluorescent radiation of lead. In the case of the Button sampler, the bias is larger, indicating a further source of error, perhaps due to the thickness of the deposit. However, in all cases, correction of the lead results did not greatly affect the overall percentage of samples where the XRF result was within 25% of the ICP result, although it did improve the overall accuracy of the results. The GSP, IOM and Button samplers are suitable candidates for further evaluation as compatible with on-site XRF analysis for lead and other metals. It is important to check carefully factory pre-set instrument calibrations, as a bias in the calibration for copper was observed.     

Design and validation of a passive deposition sampler

A new, passive particle deposition air sampler, called the Einstein-Lioy Deposition Sampler (ELDS), has been developed to fill a gap in passive sampling for near-field particle emissions. The sampler can be configured in several ways: with a protective hood for outdoor sampling, without a protective hood, and as a dust plate. In addition, there is an XRF-ready option that allows for direct sampling onto a filter-mounted XRF cartridge which can be used in conjunction with all configurations. A wind tunnel was designed and constructed to test the performance of different sampler configurations using a test dust with a known particle size distribution. The sampler configurations were also tested versus each other to evaluate whether or not the protective hood would affect the collected particle size distribution. A field study was conducted to test the sampler under actual environmental conditions and to evaluate its ability to collect samples for chemical analysis. Individual experiments for each configuration demonstrated precision of the sampler. The field experiment demonstrated the ability of the sampler to both collect mass and allow for the measurement of an environmental contaminant i.e. Cr(6+). The ELDS was demonstrated to be statistically not different for Hooded and Non-Hooded models, compared to each other and the test dust; thus, it can be used indoors and outdoors in a variety of configurations to suit the user's needs.     

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.     

A simple,cost-effective multispecies toxicity test using organisms with a cosmopolitan distribution

Difficulties in making accurate, ecosystem-level predictions of environmental effects of chemicals, mixtures, and effluents based solely on the results of tests on single species have necessitated the development of more environmentally realistic, predictive testing methods. This paper describes a multispecies, community-level toxicity test based on the colonization of artificial substrates by microbial species. Tests examined the colonization of initially barren polyurethane foam artificial substrates by Protozoa from a species source colonized in a natural system. Differences in colonization were examined in microecosystems amended with low levels of cadmium, a very toxic heavy metal, and TFM, an organic biocide used against larval sea lamprey. Tests examined differences in colonization over 28 days. For cadmium, effect levels were estimated to be near 1 g 1^–1, in the low range of effect levels determined from chronic single species tests. For TFM, effect levels were estimated to be between 1 and 10 ppm, overlapping the concentrations used in environmental applications. The colonization response, which depends on naked microbial cells reproducing and migrating through toxicant amended water to new substrates, is very sensitive. Tests based on colonization can be adapted to use species from a target receiving system or can use species from a designated natural source. Field validation of these tests can employ nearly identical methods to those used in laboratory studies to assess the accuracy of predictions based on test system data.     

A technique for cutting brittle undisturbed lateritic soil block samples

This note describes a technique for cutting undisturbed brittleblock samples into smaller specimens for further geotechnical testing. This technique revealed very useful in dealing with collapsible soils, where the sampling is recommended to be donewith block soil samples. A further use of this technique as an efficient way for sampling collapsible soils is proposed.     

Evaluation of a novel passive sampling technique for monitoring volcanogenic hydrogen sulfide

A novel, low-cost passive sampling procedure for monitoring of volcanogenic hydrogen sulfide is reported. The technique is based on absorption of H2S onto treated sections of photographic paper, which are housed in plastic film canisters during exposure. The H2S reacts with silver halide in the photographic paper, causing a colour-change reaction from white, through brown, to black, depending on concentration of atmospheric H2S. The sampler is sensitive to < 30 ppb to approximately 1000 ppb of H2S. Here we present results from a series of optimization and quantification experiments. An active sampling procedure for rapid H2S measurement is also reported, based on absorption of H2S onto Whatman No. 41 cellulose filters treated with silver nitrate, and was shown to be quantitative using a single filter at flow rates <1.0 L min(-1) for collection of <200 microg of sulfide (as H2S). Determination of sulfide collected on the substrates was performed using a rapid flow-injection technique based on the fluorescence quenching of fluorescein mercuric acetate (FMA) by sulfide. This was optimized at a FMA concentration of 8 mg L(-1), at which 100% quenching was obtained at a solution sulfide concentration of 3 mg L(-1).     

A comparison of X-ray fluorescence and wet chemical analysis for lead on air filters from different personal samplers used in a secondary lead smelter/solder manufacturer

Portable X-ray fluorescence (XRF) technology may provide faster turn-around without compromising accuracy when assessing personal exposures to metals such as lead, but it has only been tested in limited field environments. This study is part of a series, where various types of sampler are used to collect airborne lead in different environments for presentation to a portable XRF analyzer. In this case personal samples were taken at a manufacturer of solder alloys consisting mainly of lead and tin, using the closed-face 37 mm cassette (CFC), 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. Following XRF analysis the samples were extracted with acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP). The internal surfaces of CFC's and 25 mm open-face cassettes were also wiped, and the wipes analyzed for lead to assess wall-losses in these two samplers. Analysis of all elements present is useful to ascertain contributions to matrix interference effects. In addition to lead, other metals such as tin, copper, iron, silver, cadmium and antimony were also detected in some or all of the samples by ICP analysis, but only copper and iron could be determined using the XRF analyzer under test. After the removal of a few outliers, all five samplers gave good correlations (r(2) > 0.9) between the two analytical methods over the entire range of found lead mass, which encompassed both the action level and 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 without additional correction, indicating an absence of matrix effects, particularly from tin, which was the most common element after lead. The average of three XRF readings across filters from the GSP samplers gave the best results with 96.7% of results within +/-25% and 100% within +/-30% of the associated ICP values. Using the center reading only was almost as good with 90.0% of results within +/-25% and 96.7% within +/-30% of the associated ICP values, and results can be obtained faster with a single reading. The use of an algorithm developed by OSHA for three readings from the CFC filter samples gave the next best results with 93.3% of XRF results within +/-25% of the corresponding ICP values. However, analysis of wipes from the interior of the cassettes indicated a substantial loss of sample to the walls, and even larger wall-losses were encountered in the 25 mm open-face cassette. Neither this latter sampler nor the IOM or button sampler met the 95% criterion, even for +/-30% accuracy.     

Trends in background levels of persistent organic pollutants at Kosetice observatory, Czech Republic.1) Part I. Ambient air and wet deposition 1996-2005

Kosetice observatory is a facility of the Czech Hydrometeorological Institute, which is a part of the European Monitoring and Evaluation Programme (EMEP) network. Persistent organic pollutants (POPs: PCBs, DDTs, HCHs, PAHs) have been monitored in all environmental matrices using the integrated monitoring approach. Generally, the atmospheric levels of POPs in this Central European background station (mean values: 0.115 ng m(-3) for SigmaPCBs, 0.040 ng m(-3) for SigmaDDTs, 0.077 ng m(-3) for SigmaHCHs, and 17 ng m(-3) for SigmaPAHs) are significantly higher than those in other EMEP stations localized mostly in Northern and Western Europe. Long-term trends of POP concentrations in the ambient air and wet deposition are presented in this article and they show a slow decline in the last decade for most of the investigated compounds. Temporally increased levels of certain chemicals were associated with some local climatic (floods) or socio-economic (fuel prices) factors.