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.     

The equivalence of diffusive samplers to reference methods for monitoring O3, benzene and NO2 in ambient air

A study of the equivalence to the reference methods of the Radiello samplers for ozone (O(3)) and benzene as well as the membrane-closed Palmes tube (MCPT) for nitrogen dioxide (NO(2)) is presented. These samplers benefit from new model equations capable of estimating their uptake rate. For O(3), the aim here was to demonstrate the equivalence for the reference period of 8 h and 120 microg m(-3), the target value of the 3rd European Daughter Directive. For benzene, the demonstration of equivalence to the annual limit value of 5 microg m(-3) of the 2nd European Daughter Directive was examined. In the case of NO(2), the equivalence to the annual limit value of the 1st European Daughter Directive (40 microg m(-3)) was considered. Results show that the radial sampler for O(3) fails to meet the Data Quality Objective (DQO) for continuous monitoring. However, with an expanded uncertainty of less than 30%, the O(3) diffusive sampler fulfils the DQO for indicative measurements. For benzene, the Radiello sampler exposed for 7 days gave satisfying results showing the ability of the sampler to meet the DQO of the reference method. Nevertheless, the field tests should be complemented by measurements for a wider range of benzene concentrations. In the case of NO(2), all the results of the laboratory and field experiments respected the requirements necessary for the demonstration of equivalence. Overall, these findings thus show that the Radiello sampler and the MCPT are equivalent to the reference methods only for assessment of benzene and NO(2), respectively.     

Continuous, intermittent and passive sampling of airborne VOCs

Long sampling periods are often advantageous or required for measuring air quality and characterizing exposures. However, sampling periods exceeding 8 to 24 h using thermally desorbable adsorbent tube (TDT) samplers for the measurement of airborne volatile organic compounds (VOCs) face several challenges, including maintaining stable and low flow rates, and avoiding breakthrough of the adsorbent. These problems may be avoided using intermittent sampling; however, the literature contains few if any reports that have evaluated this technique in environmental, occupational or other applications. The purpose of this study is to evaluate continuous, intermittent and passive sampling methods using both laboratory and real-world tests. Laboratory tests compared continuous and intermittent (active) samplers in a controlled dynamic test gas generation system. Field tests used side-by-side active and passive samplers in an office, home workshop and four smokers' homes. All samples were analyzed for a wide range of VOCs by GC-MS. In most instances, intermittent sampling yielded better reproducibility (duplicate precision of 10 +/- 6%) than continuous low-flow sampling (18 +/- 5%), in part due to difficulty maintaining low flows. Concentrations obtained using intermittent sampling agreed with those for continuous sampling, with downward biases resulting primarily from errors in flow rate measurements. In the field, more VOC species were detected using active rather than passive sampling. Passive measurements were 12% lower than continuous measurements, a difference attributed to declining uptake rates at higher concentrations over the 3 to 4 d sampling period. Overall, most measurements obtained using the three sampling methods agreed within 20% for a wide range of concentrations (0.1 to 230 microg m(-3)). Both passive and intermittent sampling approaches are suitable for long sampling periods, but intermittent sampling provides greater flexibility with respect to sampling period, and permits the use of multi-bed adsorbents that can capture a wider range of VOCs.     

Evaluation of the effect of different sampling time periods and ambient air pollutant concentrations on the performance of the Radiello diffusive sampler for the analysis of VOCs by TD-GC/MS

The effect of different sampling exposure times and ambient air pollutant concentrations on the performance of Radiello? samplers for analysis of volatile organic compounds (VOCs) is evaluated. Quadruplicate samples of Radiello? passive tubes were taken for 3, 4, 7 and 14 days. Samples were taken indoors during February and March 2010 and outdoors during July 2010 in La Canonja (Tarragona, Spain). The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detection (MS). The results show significant differences (t-test, p < 0.05) between the amounts of VOCs obtained from the sum of two short sampling periods and a single equivalent longer sampling period for 65% of all the data. 17% of the results show significantly larger amounts of pollutant in the sum of two short sampling periods. Back diffusion due to changes in concentrations together with saturation and competitive effects between the compounds during longer sampling periods could be responsible for these differences. The other 48% of the results that are different show significantly larger amounts in the single equivalent longer sampling period. The remaining 35% of the results do not show significant differences. Although significant differences are observed in the amount of several VOCs collected over two shorter sampling intervals compared to the amount collected during a single equivalent longer sampling period, the ratios obtained are very close to unity (between 0.7 and 1.2 in 75% of cases). We conclude that Radiello? passive samplers are useful tools if their limitations are taken into account and the manufacturer's recommendations are followed.     

Field evaluation of a tailor-made new passive sampler for the determination of NO2 levels in ambient air

This study describes the field evaluation of a tailor-made new glass passive sampler developed for the determination of NO(2), based on the collection on triethanolemine (TEA)-coated fibre filter paper. The sampler has been derived from a Palmes design. The overall uncertainty of the sampler was determined by using Griess-Saltzman ASTM D 1607 standard test method as a reference method. The agreement between the results of the passive sampler and the reference method was +/-7.90% with the correlation coefficient of 0.90. Method precision in terms of coefficient of variance (CV) for three simultaneously applied passive samplers was 8.80%. The uptake rate of NO(2) was found to be 2.49 ml/min in a very good agreement with the value calculated from theory (2.63 ml/min). Sampler detection limit was 1.99 microg/m(3) for an exposure period of 1 week and the sampler can be stored safely for a period of up to 6 weeks before exposure. A comparison of the sampler performance was conducted against a commercially available diffusion tube (Gradko diffusion tube). The results from the applied statistical paired t test indicated that there was no significant difference between the performances of two passive samplers (R (2) > 0.90). Also, another statistical comparison was carried out between the dark and transparent glass passive samplers. The results from the dark-colour sampler were higher than that from the transparent sampler (approximately 25%) during the summer season because of the possible photodegradation of NO(2)-TEA complex.     

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.     

Monitoring of ozone in selected forest ecosystems in Southern Carpathian and Romanian Intensive Monitoring Network (level II)

In the Romanian forest ecosystems, the first measurements of ambient ozone (O(3)) concentrations started in 1997 in 6 of 26 locations established in a trans-Carpathian Network. Furthermore, three additional ozone and other phytotoxic pollutant (NO(x), SO(2) and NH(3)) monitoring networks were installed in 2000 in Retezat (11 locations) and during 2006-2009 in Bucegi-Piatra Craiului (22 locations) LTER Sites. Since 2007, in four Intensive Forest Monitoring plots (level II), measurements of ozone concentrations were developed. Measurements were made using the Ogawa? passive sampler system during the growing season (April to October). In the Bucegi LTER Site, the seasonal means of 42.5-47.2 ppb in 2006 and 2008 were higher than those determined in the Carpathian Network in the 1997-1999 period (39.0-42.0 ppb), while the 2009 mean of 40.0 ppb was in the range of these values. The O(3) levels were slightly higher than those measured in Retezat LTER Site. In the Intensive Forest Monitoring Network (level II), no significant differences in ozone concentrations between individual core plots were noticed. The seasonal means for each plot range between 36.8 and 49.8 ppb in 2008. An influence of ozone concentrations on crown condition and tree volume growth was not determined.     

Field Comparison of two NO2 Passive Samplers to Assess Spatial Variation

Two-week average NO₂ concentrations were measured in Amsterdam (NL), Huddersfield (UK) and Prague (CZ) at 80 sites in each study area, to assess small area spatial variation, using a tube type and a badge type passive sampler. The badges appeared to be less robust than the tubes. The lower detection limit for tubes and badges was 3.7 and 0.91 µg/m³, respectively for fortnightly measurements. Accuracy of the samplers was determined with reference methods (chemiluminescence). The mean ratio of the concentration measured by diffusion tube over that by the reference method was 1.16, 1.03 and 0.77 in Amsterdam, Huddersfield and Prague, respectively. Standardizing the badges for the results obtained in Amsterdam, the relative mean ratio of the concentration measured by the badges over that by the reference method was 0.95 and 0.58 in Huddersfield and Prague, respectively. NO₂ concentrations measured by the two designs did not differ significantly. Mean NO₂ concentrations were 36, 26 and 22 µg/m³ in Amsterdam, Huddersfield and Prague, respectively. The precision of duplicate tubes and badges was 8% and 11%, respectively. Both samplers are suitable for determining real variation in small area NO₂ concentrations in the ranges which occurred. It is concluded that low-cost, simple NO₂ passive samplers can provide reliable information about variation in NO₂ concentrations within urban or rural areas on a small spatial scale. Based on its robustness and its precision, tubes were preferred over badges.     

Laboratory and field validation of a combined NO2-SO2 Radiello passive sampler

A combined NO2-SO2 Radiello radial-type diffusive sampler was validated under controlled laboratory conditions and compared with NO2-SO2 results of 3 other type of samplers in a field comparison at two locations Ghent-Mariakerke and Borgerhout in Flanders. Laboratory exposures at different temperatures (-5, 10 and 30 degrees C) and relative humidities (0, 50 and 80% RH) in combination with varying concentration levels and exposure times were carried out, with a focus on extreme conditions. Concentration level and exposure time were changed together following suppliers linear working range of samplers and assuring absolute amounts of compounds on the sampler corresponding to those of environmental levels. The average uptake rate for NO2 for 24 hour exposures at 10 degrees C and 50% RH and tested concentration levels (+/-73, 146 and 293 ppb NO2) was 0.076 +/- 0.011 ng ppb(-1) min(-1). Uptake rates during all experiments were lower than the uptake rate given in the instruction manual of the sampler. A significant effect of temperature and relative humidity on NO2 uptake rate was observed. The temperature effect from 10 to 30 degrees C corresponds to the temperature effect given by the supplier of the samplers. High relative humidity (70 to 80%) caused a strong non-reproducible decrease of uptake rate for NO2 at 24 hour experiments but this effect was not observed at longer exposures except for the tests at -5 degrees C. At the tested temperature below zero in combination with high relative humidity the sampler showed anomalous behaviour for NO2. The possible effect of concentration level and exposure time for NO2 needs further research. The average uptake rate for SO2 calculated from all exposures is 0.478 +/- 0.075 ng of sulfate ion each ppb min of SO2 and accords to suppliers uptake rate. No clear effects of temperature, relative humidity or concentration level/exposure time on the uptake rate for SO2 were found, partly due to the large scatter of results. Although NO2 accuracy of Radiello samplers was better during field campaigns than during laboratory validation, IVL and OGAWA samplers gave better results for NO2. In the field, IVL samplers showed best agreement with the continuous analyzers for both NO2 and SO2.     

Evaluation of short-term Ogawa passive, photolytic, and federal reference method sampling devices for nitrogen oxides in El Paso and Houston, Texas

Passive Sampling Devices (PSDs) have been successfully used by government and academic agencies to monitor common ambient air pollutants such as ozone and nitrogen dioxide (NO(2)). Most PSD studies have involved long-term (e.g. bi-weekly or monthly) sampling. But the Passive Ozone Network of Dallas (POND) studies of 1998 and 1999 showed that high quality 24-hour and 12-hour data using the Ogawa PSD could be collected for ambient ozone concentrations. This paper presents an evaluation of short-term passive sampling results for nitrogen oxides (NO(x)) in El Paso and Houston, Texas, using the Ogawa PSD. The Ogawa NO(x) PSDs were compared to both Federal Reference Method (FRM) monitors and a photolytic converter, with the photolytic converter designed to report closer concentrations to "true" NO(x) by more effectively limiting the interferences of other nitrogen species. Overall, good agreement was noted for all three monitor types in both cities, supporting the potential use of lower cost Ogawa PSDs for large multi-site episodic NO(x)/NO(2)/NO saturation screening studies. This evaluation was conducted during two separate six week periods of the cooler winter months so additional testing of the Ogawa PSDs during different seasons is recommended.     

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.     

Ammonia Monitoring in Switzerland with Passive Samplers: Patterns, Determinants and Comparison with Modelled Concentrations

Gaseous ammonia (NH3) is an important form of N deposition to ecosystems, but it is not being routinely monitored in Switzerland. Therefore, a study was conducted to estimate annual means and seasonal patterns of NH3 concentrations for different site types in Switzerland, and to compare annual measured and modelled NH3 concentrations. NH3 concentrations were measured using the 'Zürcher' passive sampler, a Palmes type sampler with an acidic solution as absorbent. Twenty-four sampling sites were run for one year, and 17 for two years. The samplers were changed fortnightly or monthly. Spatial emission patterns were mapped by combining information on (1) the location of emission sources, (2) national statistics on NH3-emitting activities and (3) activity-specific emission factors. The spatial resolution was one hectare. The mean annual NH3 concentration in the ambient air of the 41 sites was 2.5+/-0.3 microg m(-3) (mean+/-standard error). It ranged from 0.4 to 7.5 microg m(-3). The site type and the season were the most important factors explaining the variation in the seasonal mean concentration. NH3 concentrations were highest in intensively used agricultural areas and in cities, and lowest in Alpine sites remote from emission sources. At 39 out of 41 sites, the NH3 concentrations were higher in summer (3.1+/-0.3 microg m(-3)) than in winter (2.0+/-0.3 microg m(-3)). Modelled NH3 concentrations did not systematically deviate from measured concentrations (r2 = 0.69). With the combined monitoring and modelling approach, it is now possible to obtain a reasonable and consolidated picture of the overall NH3 situation in Switzerland.     

Diffusive uptake in passive and active adsorbent sampling using thermal desorption tubes

Low flow active sampling techniques collecting vapors and gases using thermally desorbable adsorbents are now feasible and desirable in many applications as they permit long integration times, the potential for miniaturized sampling configurations, and other advantages. At very low air flow rates (< 1 ml min(-1)), diffusive uptake on adsorbents in conventional sorbent tubes may equal or exceed the active (pumped) uptake rate, and even at low flow rates (1-4 ml min(-1)), diffusive uptake may significantly bias measurements. Thus, corrections to account for the diffusive flux or means to limit the diffusive uptake are needed in low flow applications. This paper presents (1) a theoretical analysis of the role of diffusive and advective uptake for several sampling geometries of tube-type samplers; (2) experimental confirmation using both laboratory and field studies; (3) estimates of the tortuosity and porosity of the glass wool packing used to retain the adsorbent, parameters needed to estimate diffusive fluxes in passive and active sampling; (4) a demonstration that orifice-equipped low flow active samplers can reduce diffusive uptake and improve precision, and (5) a model predicting the saturated adsorbent layer that helps to account for the gradual decline in uptake rates seen in passive sampling. Diffusive uptake will depend on the tube configuration and diffusion coefficient of the substance of interest, but for conventional sampling tubes (0.4-0.5 cm id, 1.5 cm air gap), sample flow rates should be maintained above 1 to 4 ml min(-1) to keep errors below 5%. Laboratory experiments showed close agreement with theoretical calculations, and the field study using 1 to 4 d sampling periods and 0.3 ml min(-1) flows demonstrated that the orifice-equipped samplers essentially eliminated diffusive uptake. No significant practical difficulties are encountered using orifices, e.g., pressure drop is minimal. Experimental estimates of tortuosity (0.79 +/- 0.02) and porosity (0.92 +/- 0.10) of the glass wool packing (0.3 cm length) represent relatively little resistance to diffusion; however, variation in the packing and adsorbent placement can degrade the precision achievable by passive samplers. Diffusion barriers, consisting most simply of an orifice, may be used to lower the diffusive uptake. A needle-type orifice permits flows below 0.1 ml min(-1) and is suitable for sampling periods as long as several weeks, and it provided greater precision than conventional open-ended sampling tubes (8% compared to 13%). Finally, the gradual decrease in diffusive fluxes often seen in passive sampling is attributed to additional resistance posed by a saturated adsorbent layer, in agreement with a simple model based on total VOCs and specific adsorptivity of the adsorbent.     

A passive sampling method to determine ammonia in ambient air

Ambient ammonia concentrations, mainly originating from agricultural activities, have increased in the last few decades in Europe. As a consequence, critical loads on oligotrophic ecosystems such as forests and mires are greatly exceeded. Monitoring of ambient ammonia concentrations is necessary in order to investigate source-receptor relationships. Measuring ambient ammonia concentrations continuously with high time resolution is very expensive and cost-efficient systems are required. Where time resolution is of minor importance, several cost-effective systems, mainly dry denuder and passive samplers, can be applied. In this paper the Zürcher passive sampler, a diffusive sampling system, is presented. It is a Palmes type sampler with an acidic solution as absorbent and is easy to handle. It was tested at 46 sites in Switzerland over one year. The average concentration in ambient air was 2.5 microg m(-3) +/- 0.4 microg m(-3). The average of the blank values were 0.21 microg m(-3). The detection limit (double the standard deviation of the blank values) was 0.36 microg m(-3). Three passive samplers were exposed at each site and each period. The mean standard deviation of these triplicate measurements was 9.5%. Compared with a discontinuous tubular denuder system and a continuous annular denuder system, the deviation was less than 10%. The Zürcher passive sampler is a useful and cost-efficient tool to determine long-term average ammonia concentrations (one- to four-week periods) in ambient air for mean concentrations above 1 microg m(-3).     

Assessment of pumped mercury vapour adsorption tubes as passive samplers using a micro-exposure chamber

Mercury vapour adsorption tubes manufactured for pumped sampling and analysis have been evaluated for their performance as passive samplers. This has been done by exposing these tubes in a novel micro-exposure chamber. The uptake rates of these tubes have been found to be low (approximately 0.215 ml min(-1)) as compared to bespoke passive samplers for mercury vapour (typically in excess of 50 ml min(-1)). The measured uptake rates were shown to vary significantly between tubes and this was attributed to the variability in the air-sorbent interface and the proportion of the cross sectional area removed by the crimp in the quartz tubes used to secure the sorbent material. As a result of this variability the uptake rate of each tube must be determined using the micro-exposure chamber prior to deployment. Results have shown that the uptake rate determined in the micro-exposure chamber is invariant of concentration, and therefore these uptakes rates may be determined at a high mercury vapour concentration for many tubes at once in less than one hour. The uptake rate of the adsorption tubes under these conditions may be determined with a precision of 5%. Measurements made on a limited field trial in indoor and outdoor ambient air have shown that these tubes give results in acceptable agreement with more traditional pumped sampling methods, although longer sampling periods are required in order to reduce the uncertainty of the measurement, which is currently approximately 30%.     

Characterization and optimization of an online system for the simultaneous measurement of atmospheric water-soluble constituents in the gas and particle phases

In this work we present the results of extensive characterization and optimization of the Ambient Ion Monitor-Ion Chromatograph (AIM-IC) system, an instrument developed by URG Corp. and Dionex Inc. for simultaneous hourly measurements of the water-soluble chemical composition of atmospheric fine particulate matter (PM(2.5)) and associated precursor gases. The sampling assembly of the AIM-IC consists of an inertial particle size-selection assembly, a parallel-plate wet denuder (PPWD) for the collection of soluble gases, and a particle supersaturation chamber (PSSC) for collection of particles, in series. The analytical assembly of the AIM-IC consists of anion and cation IC units. The system detection limits were determined to be 41 ppt, 5 ppt, and 65 ppt for gas phase NH(3(g)), SO(2(g)), and HNO(3(g)) and 29 ng m(-3), 3 ng m(-3), and 45 ng m(-3) for particle phase NH(4)(+), SO(4)(2-), and NO(3)(-) respectively. From external trace gas calibrations with permeation sources, we determined that the AIM-IC is biased low for NH(3(g)) (11%), SO(2(g)) (19%), and HNO(3(g)) (12%). The collection efficiency of SO(2(g)) was found to strongly depend on the composition of the denuder solution and was found to be the most quantitative with 5 mM H(2)O(2) solution for mixing ratios as high as 107 ppb. Using a cellulose membrane in the PPWD, the system responded to changes in SO(2(g)) and HNO(3(g)) within an hour, however for NH(3(g)), the timescale can be closer to 20 h. With a nylon membrane, the instrument response time for NH(3(g)) was significantly improved, becoming comparable to the responses for SO(2(g)) and HNO(3(g)). Performance of the AIM-IC for collection and analysis of PM(2.5) was evaluated by generating known number concentrations of ammonium sulfate and ammonium nitrate particles (with an aerodynamic diameter of 300 nm) under laboratory conditions and by comparing AIM-IC measurements to measurements from a collocated Aerosol Mass Spectrometer (AMS) during a field-sampling campaign. On average, the AIM-IC and AMS measurements agreed well and captured rapid ambient concentration changes at the same time. In this work we also present a novel inlet configuration and plumbing for the AIM-IC which minimizes sampling inlet losses, reduces peak smearing due to sample carryover, and allows for tower-height sampling from the base of a research tower.     

Long-term phenol, cresols and BTEX monitoring in urban air

This paper reports the results of a long-term monitoring of benzene, toluene, ethylbenzene, xylenes (BTEX), phenol and cresols in the air of Padua during a wide period of the year 2007 using two radial passive samplers (Radiello system) equipped with BTEX- and phenol-specific cartridges. Two sites were monitored, one in the industrial area and one close to the town centre. Relevant pollution episodes have been observed during both the winter and summer periods. Benzene, together with toluene, ethylbenzene and xylenes showed their maximum concentrations during the winter season, but the secondary pollutant phenol was higher than benzene for a large period of the year when the meteorological conditions blocked the pollutants in the lower layers of the atmosphere and solar radiation increased the benzene photo-oxidation process.     

Atmospheric NO2 and NH3 deposition into a typical agro-ecosystem in Southeast China

The dry deposition of atmospheric nitrogen (including NO(2) and NH(3)) into a typical agro-ecosystem in Southeast China during 2006-2007 was estimated. Results indicated that the dry deposition velocities of NO(2) and NH(3) ranged from 0.04-0.24 cm s(-1) and 0.09-0.47 cm s(-1), respectively. The higher values appeared in the non-crop growing period. Concentrations of atmospheric NO(2) and NH(3) ranged from 24.64-104.10 μgN m(-3) and 14.40-389.6 μgN m(-3), respectively. Variation of the NH(3) mixing ratio showed a clear double-peak. NO(2) and NH(3) deposition fluxes were 74.68-80.75 kgN ha(-1), which was equivalent to 162.4 and 175.5 kg ha(-1) of urea applied in 2006-2007. The N deposition fluxes were 13.91-40.38 and 5.33-22.73 kgN ha(-1) in peanut and rice growing periods, accounting for 8.18%-40.38% and 2.13%-23.06% of N fertilizer usages, respectively. NO(2) and NH(3) deposition were significant for the red soil farmland.     

Monitoring ammonia in urban, inner alpine and pre-alpine ambient air

Passive samplers were used to monitor ammonia concentrations at rural inner alpine and pre-alpine, as well as urban, sites in Austria and Bavaria. Elevated concentrations were measured both at farms (up to 36 microg NH3 m(-3)) and at urban locations (up to 28 microg NH3 m(-3)). At urban locations a linear relationship between the traffic density and the NH3 concentration was found, but there was no marked seasonal trend. The highest ammonia concentrations were measured in a traffic tunnel (up to 78 microg NH3 m(-3)). The presence of livestock breeding or small scale alpine pastures resulted in elevated concentrations at the rural sites (8.1-12 and 2.5-4.6 microg NH3 m(-3), respectively), compared to the surrounding areas (3.1 and 0.9 microg NH3 m(-3)). Agriculture related sources are usually limited either spatially or seasonally. As the emissions were moderate in our case, a rapid removal and dilution of ammonia was possible and therefore the NH3 burden was only local. Sources related to traffic are more evenly distributed both geographically and seasonally. The WHO guideline, annual average concentration of 8 microg m(-3) for the protection of vegetation, was only exceeded at farms, at the urban station with the heaviest traffic and in the Tauerntunnel.     

Simultaneous measurement of ventilation using tracer gas techniques and VOC concentrations in homes, garages and vehicles

Air exchange rates and interzonal flows are critical ventilation parameters that affect thermal comfort, air migration, and contaminant exposure in buildings and other environments. This paper presents the development of an updated approach to measure these parameters using perfluorocarbon tracer (PFT) gases, the constant injection rate method, and adsorbent-based sampling of PFT concentrations. The design of miniature PFT sources using hexafluorotoluene and octafluorobenzene tracers, and the development and validation of an analytical GC/MS method for these tracers are described. We show that simultaneous deployment of sources and passive samplers, which is logistically advantageous, will not cause significant errors over multiday measurement periods in building, or over shorter periods in rapidly ventilated spaces like vehicle cabins. Measurement of the tracers over periods of hours to a week may be accomplished using active or passive samplers, and low method detection limits (<0.025 microg m(-3)) and high precisions (<10%) are easily achieved. The method obtains the effective air exchange rate (AER), which is relevant to characterizing long-term exposures, especially when ventilation rates are time-varying. In addition to measuring the PFT tracers, concentrations of other volatile organic compounds (VOCs) are simultaneously determined. Pilot tests in three environments (residence, garage, and vehicle cabin) demonstrate the utility of the method. The 4 day effective AER in the house was 0.20 h(-1), the 4 day AER in the attached garage was 0.80 h(-1), and 16% of the ventilation in the house migrated from the garage. The 5 h AER in a vehicle traveling at 100 km h(-1) under a low-to-medium vent condition was 92 h(-1), and this represents the highest speed test found in the literature. The method is attractive in that it simultaneously determines AERs, interzonal flows, and VOC concentrations over long and representative test periods. These measurements are practical, cost-effective, and helpful in indoor air quality and other investigations.