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).     

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.     

北欧地区大气无动力监测技术在亚热带高原的应用研究

无动力监测技术是一种成本低、效益高、灵敏而准确的空气气态污染物平均浓度监测采样方法,其连续时间覆盖可从几个小时到一个月.以月为采样周期时检测范围SO2为0.1～200μg/m3,NO2为0.1～400μg/m3,高灵敏度的检测下限可以满足低浓度背景区域内空气气态污染物的检出.其主要优点是采样器体积小、重量轻、无噪音、可重复利用、不用电、不需要技术人员、费用极低.采样器能在采样前后的常温条件下稳定几个月,因此能用于边远地区的环境监测.在检查模型计算和验证研究、健康影响评估、交通规划和绘制不同空气污染物在城市区域的高空间分辨率浓度分布图时,无动力采样器是最有价值的污染物高空间分辨率测定方法.文章所报道的是无动力采样技术的实际运用研究,是中瑞国际合作某项目的一部分,由瑞典环境科学研究院(IVL)与云南省环境监测中心站(YEMCS)共同完成.     

A novel passive water sampler for in situ sampling of antibiotics

Passive water sampling has several advantages over active methods; it provides time-integrated data, can save on time and cost compared to active methods, and yield high spatial resolution data through co-deployment of simple, cheap units. However, one problem with many sampler designs in current use is that their uptake rates for trace substances of interest are flow-rate dependent, thereby requiring calibration data and other information to enable water concentrations to be derived from the mass per sampler. However, the 'family' of samplers employing the principle of diffusive gradients in thin films (DGT) provides an in situ means of quantitatively measuring labile species in aquatic systems without field calibration. So far, this technique has only been tested and applied in inorganic substances: metals, radionuclides, nutrients, etc. Design and applications of DGT to trace organic contaminants ('o-DGT') would be of widespread interest. This study describes the laboratory testing and performance characteristics of o-DGT, with the antibiotic sulfamethoxazole (SMX) as a model compound and XAD18 as the novel binding agent. o-DGT uptake of SMX increased with time and decreased with diffusion layer thickness, confirming the principle for SMX. XAD18 showed sufficiently high capacity for SMX for routine field applications. o-DGT measurement of SMX was independent of pH (6-9) and ionic strength (0.001-0.1 M) and not affected by flow rate once above static conditions. The diffusion coefficient of SMX in the sampler was measured using an independent diffusion cell and information is presented to allow temperature correction and derivation of aqueous concentrations from deployed samplers. The potential use of o-DGT for in situ measurement of pharmaceutical antibiotics is confirmed by this study and applications are briefly discussed.     

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.     

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.     

Solvent-free sampling with di-n-butylamine for monitoring of isocyanates in air

The solvent-free sampler for airborne isocyanates consisted of a polypropylene tube with an inner wall coated with a glass fibre filter, coupled in series with a 13 mm glass fibre filter. The filters were impregnated with reagent solution containing equimolar amounts of di-n-butylamine (DBA) and acetic acid. Air sampling was performed with an air flow of 0.2 l min(-1). The formed isocyanate-DBA derivatives were determined using liquid chromatography and tandem mass spectrometry. The sampler was investigated in regard to collection principle and extraction of the formed derivatives with good results. The possibility to store the sampler before sampling and to perform long-term sampling was demonstrated. Field extraction of the sampler was not necessary, as there was no difference between immediately extracted samples and stored ones (2 days). In comparative studies, the sampler was evaluated against a reference method, impinger-filter sampling with DBA as reagent. The ratios between the results obtained with the sampler and the reference in a test chamber at a relative humidity (RH) of 45% was in the range of 83-109% for isocyanates formed during thermal decomposition of PUR. At RH 95%, the range was 72-101% with the exception of isocyanic acid. In two field evaluations, the ratios for fast curing 2,4'- and 4,4'-methylene bisphenyl diisocyanate (MDI) was in the range 81-113% and for the 3-ring MDI the range was 54-70%. For the slower curing 1,6-hexamethylene diisocyanate (HDI) and HDI isocyanurate, the ratios were in the range 78-145%. In conclusion, the solvent-free sampler is a convenient alternative in most applications to the more cumbersome impinger-filter sampler.     

Occupational and indoor air exposure to persistent organic pollutants: a review of passive sampling techniques and needs

Exposure to persistent organic pollutants (POPs) and related compounds such as PCBs, brominated flame retardants, organochlorine pesticides and PAHs is regarded as an important environmental risk factor for humans. Recently concerns about POPs resulted in the international protocol called the Stockholm Convention on POPs. Air quality standards (indoor, outdoor and occupational) for PAHs and other POPs will also be applied in the EU in the future. This will bring requirements for monitoring, to check for compliance and to reduce human exposures to POPs. This can occur from point sources and in various microenvironments, indoors, outdoors and in workplaces. Monitoring can be undertaken either by an active (pumped) method or using a passive (diffusive) air sampling (PAS) device. To date, PAS for POPs have mainly been used as integrating (long-term) samplers for ambient (outdoor) air. However, there are several reasons to develop PAS for monitoring of POPs in occupational and indoor environments. We discuss the potential advantages, limitations and developments needed, so that PAS can be used reliably and routinely indoors and in occupational settings for POPs.     

The role of hydrodynamics, matrix and sampling duration in passive sampling of polar compounds with Empore SDB-RPS disks

There is an increasing need to monitor concentrations of polar organic contaminants in the aquatic environment. Integrative passive samplers can be used to assess time weighted average aqueous concentrations, provided calibration data are available and sampling rates are known. The sampling rate depends on environmental factors, such as temperature and water flow rate. Here we introduce an apparatus to investigate the sampling properties of passive samplers using river-like flow conditions and ambient environmental matrices: river water and treated sewage effluent. As a model sampler we selected Empore SDB-RPS disks in a Chemcatcher housing. The disks were exposed for 1 to 8 days at flow rates between 0.03 and 0.4 m s(-1). Samples were analysed using a bioassay for estrogenic activity and by LC-MS-MS target analysis of the pharmaceuticals sulfamethoxazole, carbamazepine and clarithromycin. In order to assess sampling rates of SDB disks, we also measured aqueous concentrations of the pharmaceuticals. Sampling rates increased with increasing flow rate and this relationship was not affected by the environmental matrix. However, SDB disks were only sampling in the integrative mode at low flow rates <0.1 m s(-1) and/or for short sampling times. The duration of linear uptake was particularly short for sulfamethoxazole (1 day) and longer for clarithromycin (5 days). At 0.03 m s(-1) and 12-14 degrees C, the sampling rate of SDB disks was 0.09 L day(-1) for clarithromycin, 0.14 L day(-1) for sulfamethoxazole and 0.25 L day(-1) for carbamazepine. The results show that under controlled conditions, SDB disks can be effectively used as passive sampling devices.     

Performances and application of a passive sampling method for the simultaneous determination of nitrogen dioxide and sulfur dioxide in ambient air

The performances and applicability of a diffusion tubesampler for the simultaneous measurements of NO₂ andSO₂ in ambient air were evaluated. SO₂ andNO₂are collected by the passive sampler using triethanolamine astrapping agent and are determined as sulphate and nitrite withion chromatography. The detection limit (2.3 g m^-3 ofNO₂ and 4.2 g m^-3 of SO₂ for two weekssampling) is adequate for the determination of concentrationsin urban and industrial areas. Precision of the method as RSDis in mean 5% for NO₂ and 12% for SO₂ at theconcentration levels in urban areas. Calibration of the methodwas performed in the field conditions by comparison between theresponses of sampler and the concentrations measured by thecontinuous monitors. High degree of linearity (correlationcoefficients > 0.8) is found between the passive sampler tubeand the continuous monitor data for both NO₂ and SO₂.To reduce the wind velocity influence on passive sampling ofdiffusion tubes, a protective shelter was tested in this study.The overall uncertainty of one measure for the optimised methodis estimated at 5 g m^-3 for NO₂ and 6g m^-3 for SO₂. Suitability of this passivesampling method for air pollution monitoring in urban areas wasdemonstrated by the results shown in this paper on a campaigncarried out in the French agglomeration.     

Microsoft Word for Windows在环境质量报告书中的应用

叙述了ＭｉｃｒｏｓｏｆｔＷｏｒｄｆｏｒＷｉｎｄｏｗｓ软件在编写环境质量报告书中的应用内容。     

Indoor NO2 pollution and personal exposure to NO2 in two areas with different outdoor NO2 pollution

Indoor NO₂ concentrations were measured in the kitchen, the living room and bedroom of 612 houses in two different areas in the Netherlands. In a group of housewives living in these homes, personal exposure to NO₂ was measured. NO₂ concentrations indoors were dependent on the presence or absence of (un)vented gas appliances. Personal NO₂ exposure was only different between the two areas in the group with the lowest indoor concentrations. In this study, it was determined that gas appliances inside the house are the most important factor with respect to NO₂ exposure and that outside NO₂ concentration played a secondary role, except in situations where gas appliances were absent.     

Performance of an in situ passive sampling system for metals in stormwater

A passive sampler has been developed and is demonstrated in situ for urban runoff. The passive sampler is compared to conventional composite (time-dependent and flow-weighted) bottle sampling during and between storm events. The sampling was carried out at established stormwater stations; before and after a stormwater detention pond. In situ deployment of the passive sampler provides the metal concentrations, corresponding to the electrochemically available fraction of total metal, for time-dependent samples collected in parallel. The sampler provides improved accuracy compared to bottle sampling because contamination during sample transport and handling is minimised. Laboratory handling is reduced by direct analysis of the accumulated metals on the receiving membrane by laser ablation inductively coupled plasma mass spectrometry. Passive sampling also solves the problem of metal speciation change during transport to the laboratory, which is a potential problem for bottle samples. The low cost and convenience of the passive sampler and subsequent analysis should allow significantly more extensive spatial and temporal monitoring of metals in the aquatic environment than has previously been possible.     

Using improved neural network model to analyze RSP,NOx and NO2 levels in urban air in Mong Kok,Hong Kong

As the health impact of air pollutants existing in ambient addresses much attention in recent years, forecasting of airpollutant parameters becomes an important and popular topic inenvironmental science. Airborne pollution is a serious, and willbe a major problem in Hong Kong within the next few years. InHong Kong, Respirable Suspended Particulate (RSP) and NitrogenOxides NO_x and NO₂ are major air pollutants due to thedominant diesel fuel usage by public transportation and heavyvehicles. Hence, the investigation and prediction of the influence and the tendency of these pollutants are ofsignificance to public and the city image. The multi-layerperceptron (MLP) neural network is regarded as a reliable andcost-effective method to achieve such tasks. The works presentedhere involve developing an improved neural network model, whichcombines the principal component analysis (PCA) technique and theradial basis function (RBF) network, and forecasting thepollutant levels and tendencies based in the recorded data. Inthe study, the PCA is firstly used to reduce and orthogonalizethe original input variables (data), these treated variables arethen used as new input vectors in RBF neural network modelestablished for forecasting the pollutant tendencies. Comparingwith the general neural network models, the proposed modelpossesses simpler network architecture, faster training speed,and more satisfactory predicting performance. This improvedmodel is evaluated by using hourly time series of RSP, NO_x and NO₂ concentrations collected at Mong Kok Roadside Gaseous Monitory Station in Hong Kong during the year 2000. By comparing the predicted RSP, NO_x and NO₂ concentrationswith the actual data of these pollutants recorded at the monitorystation, the effectiveness of the proposed model has been proven.Therefore, in authors' opinion, the model presented in the paper is a potential tool in forecasting air quality parameters and hasadvantages over the traditional neural network methods.     

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.     

Indoor and outdoor air concentrations of BTEX and NO2: correlation of repeated measurements

Studies on health effects of air pollutants ideally define exposure through the collection of air samples in the participants' homes. Concentrations derived from these samples are then considered as an estimate for the average concentration of air pollutants in the homes. Conclusions drawn from such studies therefore depend very much on the validity of the measured air pollution concentrations. In this paper we analysed repeated BTEX and NO(2) measurements with a time period of several months lying between the two conducted home visits. We investigated the variability of their concentrations over time by determining correlation coefficients and calculating within- and between-home variances. Our population consisted of 631 homes of participants from two cohort studies within the framework of the German study on Indoor Factors and Genetics in Asthma. Air pollutants were measured using passive samplers both indoors and outdoors. The measured BTEX concentrations were poorly correlated, with Pearson's correlation coefficient r ranging from -0.19 to 0.27. Additionally, a considerable seasonal effect could be observed. A higher correlation was found for the NO(2) concentrations with r ranging between 0.24 and 0.55. For the BTEX, the between-home variance was bigger than the within-home variance, for NO(2) both variances were of about the same order. Our results indicate that in a setting of moderate climate like in Germany, the variability of BTEX and NO(2) concentrations over time is high and a single measurement is a poor surrogate for the long-term concentrations of these air pollutants.     

TEA(三乙醇胺)挂片测定空气中NO2的滤膜制备方法

介绍了一种用于TEA挂片测定NO2的滤膜制备方法,解决了原方法中存在的滤膜空白值偏高且不稳定的问题.实验结果表明,该方法可用于大面积、多点位同步监侧中大批量滤膜的制备.     

Passive sampling of glycol ethers and their acetates in indoor air

This study examined the performances of a thermal desorbable radial diffusive sampler for the weekly measurement of eight glycol ethers in indoor air and described the results of an application of this method carried out as part of HABIT'AIR Nord - Pas de Calais program for the air monitoring of these compounds in sixty homes located in northern France. The target compounds were the four glycol ethers banned from sale to the public in France since the 1990s (i.e. 2-methoxy ethanol, 2-ethoxy ethanol and their acetates) and four other glycol ethers derivatives of which the use have increased considerably (i.e. 1-methoxy-2-propanol, 2-butoxy ethanol and their acetates).A test program was carried out with the aim of validating the passive sampling method. It allowed the estimation of all the parameters of a method for each compound (calibration, analytical precision, desorption efficiency, sampling rate in standard conditions, detection limit and stability of sample before and after exposure), the examination of the influence of environmental factors on the sampling rate by some exposure chamber experiments and the assessment of the uncertainty of the measurements.The results of this evaluation demonstrated that the method has turned out to be suitable for six out of eight glycol ethers tested. The effect of the environmental factors on the sampling rates was the main source of measurement uncertainty. The measurements done in sixty homes revealed a relative abundance of 1-methoxy-2-propanol that was found in more than two thirds of homes at concentration levels of 4.5 microg m(-3) on average (a maximum value of 28 microg m(-3)). 1-methoxy-2-propanol acetate and 2-butoxy ethanol were also detected, but less frequently (in 19% of homes) and with the concentrations below 12 microg m(-3). The highest levels of these glycol ethers appear to be in relation to the emissions occurring at the time of cleaning tasks.     

Effect-based assessment of passive air samples from four countries in Eastern Europe

Although passive sampling has been previously used for the monitoring of volatile and semi-volatile contaminants in air, there are limited data on the use of this technique coupled with bioassays based on specific biological responses. Biological responses including those mediated by the aryl hydrocarbon (AhR) receptor as well as (anti-)estrogenicity and (anti-)androgenicity of samples from four Eastern European countries (Lithuania, Slovakia, Romania, and Serbia) were determined. To address the potential differences of specific toxic potencies of pollutant mixtures in ambient air in Eastern Europe, each country was characterized by a single more remote location that served to determine regional background conditions and one location in more urbanized and industrialized locations, which were defined as “impacted” areas. Besides samples from Lithuania, a significant gradient in concentrations of AhR-mediated potency from background and impacted localities was observed. Greatest potencies were measured in samples from impacted locations in Romania and Slovakia. Concentrations of polycyclic aromatic hydrocarbons (PAHs) that were quantified accounted for 3–33 % of the 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents determined by use of the bioassay. No significant estrogenic potency was detected but anti-estrogenic effects were produced by air from two background locations (Lithuania, Slovakia) and three impacted locations (Lithuania, Romania, and Serbia). Anti-androgenic potency was observed in all samples. The greatest anti-estrogenic potency was observed at the background location in Slovakia. Anti-estrogenic and anti-androgenic potencies of studied air samples were probably associated with compounds that are not routinely monitored. The study documents suitability of passive air sampling for the assessment of specific toxic potencies of ambient air pollutants.     

Effect of sample flow rate and sampling duration on the absorption of NO2 in the sodium arsenite monitoring method

The effect of the two most critical parameters, the sample flow rate and sampling duration, on the absorption efficiency of NO2 in the sodium arsenite method of nitrogen dioxide determination in ambient air was studied. Laboratory experiments showed a high sensitivity to these parameters, which were subjected to variation during actual field monitoring. The reported NO2 absorption efficiency of the method of 82% at a flow rate of 0.2 l min-1 was found to be as low as 33% at a flow rate of 1.0 l min-1 for a sampling duration of 24 h. Similarly, a considerable decrease in absorption efficiency with increasing sampling duration from 2 to 24 h was observed at a particular flow rate. Correction factors for the absorption efficiency were evolved that can be used to update the existing database, as well as future NO2 data generated using this manual monitoring method.