Field comparison of passive samplers versus UV-photometric analyser to measure surface ozone in a Mediterranean area

The aim of the present work is to compare the performance of the Radiello passive sampler versus UV-photometric ozone analyser to measure surface ozone in a Mediterranean Spanish coastal area. The comparison presented considers precision, bias, accuracy, selectivity, detection limit, cost and applicability. For assessing precision, co-located samplers were exposed in duplicate in two reference-sampling sites, beside UV-photometric ozone analyser. Bias was calculated comparing results of passive samplers exposed in three reference-sampling sites and two contrast-sampling sites with the measurements given by the reference analysers. Accuracy was calculated following the EN 482:1994 standard. The limit of detection was calculated as 3 times the standard deviation of the blanks in a batch of passive samplers. The compared Radiello passive samplers give a precision of 5.2%, a bias of 13.8%, an accuracy of 20.5% and a limit of detection of 12.6 microg m(-3). The selectivity and applicability of this methodology is in both aspects successful. Surface ozone levels measured with passive samplers were comparable with the averaged values measured with the reference analyser both in the reference-sampling sites and in the contrast-sampling sites.     

Identifying the origin of atmospheric inputs of trace elements in the Prades Mountains (Catalonia) with bryophytes, lichens, and soil monitoring

The biomonitors Hypnum cupressiforme and Xanthoria parietina were used to assess the deposition of trace elements and their possible origin in the Prades Mountains, a protected Mediterranean forest area of NE Spain with several pollution sources nearby. Al, As, Cd, Co, Cu, Cr, Ni, Pb, Sb, Ti, V, and Zn were determined in 16 locations within this protected area. Soil trace element concentrations were also ascertained to calculate enrichment factors (EF) and use them to distinguish airborne from soilborne trace element inputs. In addition, lichen richness was measured to further assess atmospheric pollution. EF demonstrated to be useful not only for the moss but also for the lichen. Cd, Cr, Cu, Ni, and Zn presented values higher than three in both biomonitors. These trace elements were also the main ones emitted by the potential sources of pollutants. The distance between sampling locations and potential pollution sources was correlated with the concentrations of Cu, Sb, and Zn in the moss and with Cr, Ni, and Sb in the lichen. Lichen richness was negatively correlated with lichen Cu, Pb, and V concentrations on dry weight basis. The study reflected the remarkable influence that the pollution sources have on the presence of trace elements and on lichen species community composition in this natural area. The study highlights the value of combining the use of biomonitors, enrichment factors, and lichen diversity for pollution assessment to reach a better overview of both trace elements’ impact and the localization of their sources.     

Atmospheric Volatile Organic Compound Monitoring. Ozone Induced Artefact Formation

Assessment of population exposure to VOC in ambient atmospheres is receiving heightened interest as the adverse health effects of chronic exposure to certain of these compounds are identified. Active (pumped) and passive samplers are the most commonly used devices for this type of monitoring. It has been shown, however, that these devices, along with all other preconcentration techniques, are susceptible to ozone interference. It is demonstrated that this interference occurs even at low ozone concentrations and that it may result in the under-estimation of population exposure. A convenient and effective ozone scrubbing method is identified and successfully applied and validated for both active and passive samplers for a range of VOC.     

A simple linear model for estimating ozone AOT40 at forest sites from raw passive sampling data

A rapid, empirical method is described for estimating weekly AOT40 from ozone concentrations measured with passive samplers at forest sites. The method is based on linear regression and was developed after three years of measurements in Trentino (northern Italy). It was tested against an independent set of data from passive sampler sites across Italy. It provides good weekly estimates compared with those measured by conventional monitors (0.85 ≤R(2)≤ 0.970; 97 ≤ RMSE ≤ 302). Estimates obtained using passive sampling at forest sites are comparable to those obtained by another estimation method based on modelling hourly concentrations (R(2) = 0.94; 131 ≤ RMSE ≤ 351). Regression coefficients of passive sampling are similar to those obtained with conventional monitors at forest sites. Testing against an independent dataset generated by passive sampling provided similar results (0.86 ≤R(2)≤ 0.99; 65 ≤ RMSE ≤ 478). Errors tend to accumulate when weekly AOT40 estimates are summed to obtain the total AOT40 over the May-July period, and the median deviation between the two estimation methods based on passive sampling is 11%. The method proposed does not require any assumptions, complex calculation or modelling technique, and can be useful when other estimation methods are not feasible, either in principle or in practice. However, the method is not useful when estimates of hourly concentrations are of interest.     

被动采样监测环境空气中SO 2和NO 2

用自主研制的采样管开展环境空气中SO2和NO2的被动采样监测.结果表明,被动采样监测结果与自动监测结果高度相关,经回归方程修正后,两者的结果没有显著性差异,被动采样的采样和分析产生的误差得以消除.     

Baseline ambient gaseous ammonia concentrations in the Four Corners area and eastern Oklahoma, USA

Ambient ammonia monitoring using Ogawa passive samplers was conducted in the Four Corners area and eastern Oklahoma, USA during 2007. The resulting data will be useful in the multipollutant management of ozone, nitrogen oxides, and visibility (atmospheric regional haze) in the Four Corners area, an area with growing oil/gas production and increasing coal-based power plant construction. The passive monitoring data also add new ambient ammonia concentration information for the U.S. and will be useful to scientists involved in present and future visibility modeling exercises. Three week integrated passive ammonia samples were taken at five sites in the Four Corners area and two sites in eastern Oklahoma from December, 2006 through December, 2007 (January, 2008 for two sites). Results show significantly higher regional background ammonia concentrations in eastern Oklahoma (1.8 parts per billion (ppb) arithmetic mean) compared to the Four Corners area (0.2 ppb arithmetic mean). Annual mean ammonia concentrations for all Four Corners area sites for the 2007 study ranged from 0.2 ppb to 1.5 ppb. Peak ambient ammonia concentrations occurred in the spring and summer in both areas. The passive samplers deployed at the Stilwell, Oklahoma site compared favorably with other passive samplers and a continuous ammonia monitoring instrument.     

Calibration of two passive air sampler configurations for monitoring concentrations of hexabromocyclododecanes in indoor air

While polyurethane foam (PUF) disk passive air samplers are employed increasingly to monitor persistent organic pollutants in indoor air, they essentially sample only the vapour phase. As a previous investigation of the vapour : particle phase partitioning of hexabromocyclododecanes HBCDs in (outdoor) air reported them to be present largely in the particulate phase, we monitored three offices using active air samplers. In each, approximately 65% of HBCDs were present in the vapour phase, suggesting PUF disk passive samplers are suitable for monitoring HBCDs in indoor air. Concentrations in the three offices (239-359 pg Sigma HBCD m(-3)) exceed substantially those reported in outdoor air from the United States (2.1-11 pg Sigma HBCD m(-3)), but are in line with outdoor air from Stockholm. The relative abundance of the three principal diastereomers in office air was closer to that found in technical HBCD formulations (i.e. predominantly gamma-HBCD) than in most US outdoor air samples. Time integrated air concentrations of alpha-, beta-, and gamma-HBCD were obtained for an office using a low volume sampler operated over a 50 d period alongside PUF disk samplers. This calibration exercise yielded the following passive air sampling rates for both a fully- and part-sheltered PUF disk sampler design: for alpha-, beta-, and gamma-HBCD, 0.87, 0.89, and 0.91 m3 d(-1) respectively (fully-sheltered) and 1.38, 1.54, and 1.55 m3 d(-1) respectively (part-sheltered). Deployment of the part-sheltered configuration yielded concentrations approximately 35% lower than those obtained using a high volume sampler, consistent with PUF disk samplers measuring primarily the vapour phase.     

Measurement of environmental pollutants using passive sampling devices--a commentary on the current state of the art

Passive sampling devices have been used since the 1970s to measure time-weighted average (TWA) or equilibrium concentrations of pollutants in various environmental matrices (e.g. air, soils and sediments and water). In recent years the popularity of using such samplers has increased and the technology in now well established for the measurement of atmospheric pollutants. This sector has a long experience of using passive samplers in the short- and long-term assessment of air quality in the local environment and on a global scale (e.g. within the United Nations Stockholm Convention on the trans-boundary movement of persistent organic pollutants (POPs) where large networks of samplers on a continental scale have been established). In comparison, the use of passive samplers for monitoring the aquatic environment has been slower to take off. There has, however, been a recent research drive to develop devices for measuring the wide range of pollutants that can be found in environmental waters (e.g. ground, surface, and marine). It is now being recognised that passive samplers can play a valuable role in monitoring water quality within a legislative framework such as the European Union's Water Framework Directive (WFD). The data from these devices can be used alongside the results obtained from conventional spot or bottle sampling to improve risk assessments and to inform decisions on undertaking potentially expensive remedial actions. Such monitoring techniques may have uses within the European Registration, Evaluation, Authorisation & restriction of CHemicals (REACH) Directive and the forthcoming European Marine Strategy Directive. It is expected that the aquatic monitoring sector will follow a transition similar to that which occurred in air monitoring where data obtained from passive samplers can use used within a legal framework. There has also been increased interest in extending the role of passive samplers to both the measurement of equilibrium concentrations and investigating the movement and release of the dissolved fraction of various pollutants in the pore water of sediments and soils.     

Errors in ozone risk assessment using standard conditions for converting ozone concentrations obtained by passive samplers in mountain regions

Passive samplers are often employed to measure ozone concentrations in remote areas such as mountain forests. The potential ozone risk for vegetation is then assessed by calculating the AOT40 exposure index (accumulated hourly ozone concentration exceedances above 40 ppb, i.e. AOT40 = Σ([O(3)] - 40)Δt for any hourly ozone concentration [O(3)] > 40 ppb). AOT40 is customary calculated on the basis of ozone concentrations expressed as a volumetric mixing ratio, while lab sheets normally report ozone concentrations from passive samplers in mass units per cubic metre. Concentrations are usually converted from mass units to ppb using a standard conversion factor taking SATP (Standard Ambient Temperature and Pressure) conditions into account. These conditions, however, can vary considerably with elevation. As a consequence, the blanket application of a standard conversion factor may lead to substantial errors in reporting and mapping ozone concentrations and therefore in assessing potential ozone risk in mountain regions. In this paper we carry out a sensitivity analysis of the effects of uncertainties in estimations of air temperature (T) and atmospheric pressure (P) on the concentration conversion factor, and present two examples from two monitoring and mapping exercises carried out in the Italian Alps. We derived P and T at each site from adiabatic lapse rates for temperature and pressure and analysed the magnitude of error in concentration estimations. Results show that the concentration conversion is much more sensitive to uncertainties in P gradient estimation than to air temperature errors. The concentration conversion factor (cf) deviates 5% from the standard transformation at an elevation of 500 m asl. As a consequence, the standard estimated AOT40 at this elevation is about 13% less than the actual value. AOT40 was found to be underestimated by an average between 25% and 34% at typical elevations of mountain forest stands in the Italian Alps when a correct conversion factor for transforming ozone concentrations from μg m(-3) to ppb is not applied.     

The ability of biological and organic synthetic materials to accumulate atmospheric particulates containing copper, lead, nickel and strontium

This work was aimed at finding materials that could be used as alternatives to lichens as air quality monitors since the high natural variability and the large amount of lichen collected are two drawbacks of the use of these organisms. Lichen Flavoparmelia caperata(L.) Hale was exposed in three different forms (transplant, detached from the substratum and as a biomass-ground and homogeneized) and compared to the planetree bark (Platanus hybrida Brot.), exposed as a biomass, and two organic synthetic materials (Chelex(R) 100 resin and cellulose acetate). Materials were exposed for two months in the winter, spring and summer, at three Portuguese coastal cities. The results showed that the airborne accumulations of Cu, Ni, Pb and Sr were partially dependent on the meteorological conditions but mainly dependent on the nature of the exposed material. The standard deviations of the synthetic materials or homogenized biomass were the same or greater than lichen transplants or detached. The accumulation by biological materials, of the four studied elements, was comparable to the lichen transplant accumulation. The replacement of the traditional transplants by the biomass was not considered advantageous, since their preparation is time-consuming. Therefore lichens remain the most suitable in biomonitoring studies. The exposure of detached lichen allows the accurate measurement of the exposed area/volume so it can be useful to relate atmospheric deposition rates with the lichen metal content. The synthetic materials accumulated Cu and Ni and should only be used as an alternative to traditional transplants when these are the elements of interest.     

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/? (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd???Cu?>?Ag?>?Cr?≥?Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.     

A New All Season Passive Sampling System for Monitoring Ozone in Air

A new all season passive sampling system for monitoring O₃ in the atmosphere has been developed in the laboratory and validated in the field. The unique features for this system include a newly designed passive sampler and a rain shelter, which allow the passive sampler to be installed in the field facing downwards. An equation associated with meteorological parameters is used to calculate the passive sampling rates. This system has been extensively tested in the lab (temperature from –18 to 20°C, relative humidity from 13 to 81%, and wind speed from 0.5 to 150 cm/s) and validated in the field in climates of all seasons. The accuracy of the ozone concentrations in the atmosphere obtained with the use of the new passive sampling system was higher than 85% compared to those obtained with continuous ozone analyzers. The new ozone passive sampling system can be used to measure ambient O₃ concentrations ranging from 3 ppb to 1000 ppb based on one-day exposure and 0.1 ppb to 140 ppb for a monthly exposure period. It is also reasonable to conclude that the new passive sampling system can be used for eight-hour exposure study because of the low field blanks and high sampling rates.     

Soil Contribution to the Elemental Composition of Epiphytic Lichens (Tuscany, Central Italy)

Total concentrations of Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sr, Ti, V and Zn in the epiphytic lichen Parmelia sulcata and superficial soils from 60 remote sampling sites in Tuscany (central Italy) were determined to evaluate the contribution of soil to the elemental composition of the lichen. The results showed that in the Mediterranean environment, the trace element content of unwashed lichen samples is greatly affected by soil contamination. However, despite the strong correlations between the concentrations of lithogene elements such as Al, Fe and Ti in P. sulcata, lichen levels of these elements were not at all linearly correlated with their concentrations in the soil, suggesting that dust contamination is highly variable and probably dependent on local site characteristics. All methods evaluated to minimize soil contamination indicated Cu, Pb and Zn as elements of atmospheric origin. However, while levels of Pb were similar to those reported for background areas, moderate pollution by Cu and Zn, probably from fertilizers used in agriculture, was revealed. For elements such as Cd and Mo, identified as atmophile, some uncertainty exists due to the fact that they are essential for lichen metabolism and accumulate intracellularly in lichens; they may therefore occur in soluble form in the lichen thallus.     

Exposure estimates for the Houston Area Asthma Study

Procedures for determining exposure extimates for the Houston Area Asthma Study are discussed. Two residential clusters of asthmatics in the Houston area have been studied as part of an overall attempt to assess the health effects of air pollution in the Texas Gulf Coast area. Air pollutant exposure data have been produced according to a three-tier monitoring scheme, i.e. (1) continuous data from centrally-located fixed stations, (2) residential indoor/outdoor measurements, and (3) personal monitoring. This air monitoring network should yield estimates of individual exposures for use in health effect correlations.The fixed sites and mobile continuously monitor ambient levels of ozone, nitrogen oxides, sulfur dioxide, carbon monoxide, and meteorological parameters (wind speed, wind direction, temperature, dew point, solar irradiation, and precipitation). Continuous sequential integrated sampling is preformed for total suspended particulates (TSP) and, inhalable particulates (IP) (total of < 2.5m and 2.5–15.0 m) by dichotomous samplers for 24 hr samplers), aldehydes (bubblers), and aeroallergens (intermittent rotorod samplers). In addition to gravimetric determinations, particulate filters are routinely analyzed for sulfate, nitrate, and (every third day) trace elements. Personal monitoring includes ozone, respirable particles, nitrogen dioxide and formaldehyde. A quality assurance/control program that meets specifications established in the EPA Quality Assurance Handbook for air pollution measurement systems was implemented. Examples of results consisting of unvalidated preliminary data from the monitoring for ozone for three participants is presented and approaches to determining exposure estimates are discussed for both an integrated exposure estimate and short time period exposure estimate.(These studies have been funded by the U.S. Environmental Protection Agency through Cooperative Agreement CR 807108010 and Grant R 808738010. Statements made in this article should not be taken as Agency policy.)     

Bioaccumulation of Trace Elements in a Wild Grass Three Years After the Aznalcóllar Mine Spill (South Spain)

In this paper, we surveyed the concentration of nine trace elements (As, Cd, Cu, Fe, Mn, Ni, Pb, Tl and Zn) in bermudagrass (Cynodon dactylon) 3 years after the mine spill in Aznalcóllar (south Spain). The results were compared with those that had been obtained for the same species in a previous study, 18 months after the accident. Three types of soil condition were determined: i) unaffected soils (UN, control); ii) cleaned up and amended soils (A, amended); and (iii) non-amended soils, inaccessible to the clean-up and remediation operations (NA, non-amended). The trace element concentrations in the plants were lower than those reported in the first sampling for both washed (plant tissues) and unwashed plants (as consumed by herbivores). Apart from Cd, trace elements concentrations (plant tissues) were similar in the A and the UN soils. In the NA soils, the Cd, Fe, Mn, Zn and Pb levels in unwashed plants were excessive for animal consumption. This wild grass seems to be suitable as a soil stabilizer for spill affected soils and as a biomonitor for soil pollution by some trace elements (As, Cu and Zn); however, its potential for phytoextraction is negligible.     

Lettuce plants as bioaccumulators of trace elements in a community of central Italy

A survey, based on the use of vascular plants to describe the distribution of selected elements (21 in total) was performed in 11 sites in the area of Castelfiorentino (Tuscany, Central Italy) differing for land use, from urban to industrial and rural areas. Lettuce plants grown under standardized conditions were positively used as biodeposimeters of airborne trace elements. Washing was found to be highly significant in reducing concentrations of many elements in the samples, suggesting a general surface contamination of leaves. The typical crustal element Al showed good correlations with Co, Fe, Li and V; on the contrary, Zn and Cd were intercorrelated and showed no connection with crustal indicators. Lead was still a relevant environmental presence, as the experiments were carried out before the ban of leaded gasoline. Source apportionment by factor analysis put in evidence a major contribution of crustal materials, followed by man-related activities; a minor role was ascertained for marine aerosol. A comparison was made between analytical data of lettuce plants grown in our experimental sites and a bulk of commercial lettuce purchased at a local supermarket. It should be stressed how Cu concentrations of commercial material were significantly higher than those found in our plants; this is likely caused by phytosanitary treatments.     

Silver near municipal wastewater discharges into western Lake Ontario,Canada

Because of the widespread use of silver nanoparticles in commercial products, discharges of municipal wastewater may be a point source of silver in the aquatic environment. We monitored two sites in western Lake Ontario impacted by discharges from wastewater treatment plants serving the City of Toronto. Concentrations of silver were elevated in bottom sediments and suspended sediments collected at the two sites. We also deployed two types of passive samplers in the water column at the two sites, the newly developed Carbon Nanotube Integrative Samplers for monitoring “CNIS-labile” silver and Diffusive Gradient in Thin Film samplers for monitoring “DGT-labile” silver. Results from these passive samplers indicated that the concentrations of silver at the two sites were either below detection limits or were in the ng/L range. In laboratory experiments where the sediments were re-suspended in Milli-Q water, a small proportion of the silver (i.e., <?25%) was labile and partitioned as colloidal or dissolved silver into the liquid phase after agitation. Nanoparticles tentatively identified as silver nanoparticles were detected by single-particle ICP-MS in suspension after agitation of both suspended and bottom sediments. Therefore, there is a need to assess whether silver species, including silver nanoparticles are transported from wastewater treatment plants into sediments in the aquatic environment. This study is unique in focusing on the in situ distribution of silver in natural waters and in sediments that are potentially impacted by urban sources of nanoparticles.     

Novel integrative passive samplers for the long-term monitoring of semivolatile organic air pollutants

Two types of passive sampler were developed for the long-term monitoring of semivolatile organic compounds (SOCs) in air. They consist of poly(dimethylsiloxane) (PDMS)-coated stir bars (type A) or silicone tubing (type B), acting as a solid receiving medium, enclosed in a heat-sealed low-density polyethylene (LDPE) membrane. These samplers combine the advantages of integrative passive sampling with those of analysing accumulated analytes by thermodesorption-GC-MS, whilst avoiding the use of solvents and expensive sample preparation and cleanup steps. The performance of these samplers was investigated for the integrative sampling of SOCs, including alpha- and gamma-hexachlorocyclohexanes, hexachlorobenzene, 2,4,4'-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl and fluoranthene, in laboratory exposure experiments under controlled conditions. For both types of sampler, the uptake of all the analytes investigated was linear over an exposure period of 15 days. The sampling rates calculated ranged from 70 to 320 ml h(-1) (sampler A) and 630 to 4300 ml h(-1) (sampler B). The passive samplers are able to detect low time-weighted average air concentrations in the pg m(-3) range. The small, robust and inexpensive sampling devices were tested successfully for the long-term air monitoring of semivolatile organic pollutants in a polluted area over an exposure period of up to 28 days.