A positive chemical ionization GC/MS method for the determination of airborne ethylene glycol and propylene glycols in non-occupational environments

An analytical method for ethylene glycol and propylene glycols has been developed for measuring airborne levels of these chemicals in non-occupational environments such as residences and office buildings. The analytes were collected on charcoal tubes, solvent extracted, and analyzed by gas chromatography-mass spectrometry using a positive chemical ionization technique. The method had a method detection limit of 0.07 microg m(-3) for ethylene glycol and 0.03 microg m(-3) for 1,2- and 1,3-propylene glycols, respectively, based on a 1.44 m3 sampling volume. Indoor air samples of several residential homes and other indoor environments have been analyzed. The median concentrations of ethylene glycol and 1,2-propylene glycol in nine residential indoor air samples were 53 microg m(-3) and 13 microg m(-3) respectively with maximum values of 223 microg m(-3) and 25 microg m(-3) detected for ethylene glycol and 1,2-propylene glycol respectively. The concentrations of these two chemicals in one office and two laboratories were at low microg m(-3) levels. The maximum concentration of 1,3-propylene glycol detected in indoor air was 0.1 microg m(-3).     

Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

Analysis of indoor gaseous formic and acetic acid, using radial diffusive samplers

A diffusive sampling method for the determination of gaseous acetic and formic acids, using a radial symmetry diffusive sampler, has been optimised for a 7-day exposure time in this study. Sampling rate determinations were performed on data obtained from a dynamic exposure chamber, simulating the indoor conditions of an empty, closed, room, at room temperature and minimal wind speed. Analysis has been performed by means of ion chromatography. The sampling rates for formic acid concentrations of 128 microg m(-3) and 1248 microg m(-3) were determined to be 91.2 +/- 3.9 ml min(-1) and 111.6 +/- 2.8 ml min(-1), respectively. The acetic acid sampling rate was independent of the concentration in the range 160 microg m(-3)-1564 microg m(-3), and amounted to 97.3 +/- 3.1 ml min(-1). Experimentally determined sampling rates showed deviations of 3% for acetic acid, and 3-21% for formic acid, in relation to theoretically derived values. The blank values were as low as 1.69 +/- 0.07 microg for formic acid and 1.21 +/- 0.14 microg for acetic acid, and detection limits lower than 0.5 microg m(-3) could be achieved, which is an improvement of 98-99% compared to previously validated diffusive sampling methods. This study describes the first step of an extended validation program in which the applicability of these types of samplers for the measurement of organic acids will be validated and optimised for the environmental conditions typical for museum showcases.     

Temporal variations of airborne particle concentration in an arid region

Airborne particle concentration (APC) measurements were carried out at the Sede Boker experimental station located in the northern Negev Desert, about 50 km south of Beer Sheva, during the years 1987--1997. The basic sampling period used in 1987--1993 was 12 h (day and night) and in 1994--1997 the sampling period was 24 h. For the entire study period, the average airborne particle concentration (APC) was 123.8 microg/m3, the highest value was 4204.2 microg/m3; and the lowest, near 5 microg/m3. For the 24 h average, about 90% of the cases were defined as normal situations (APC between 0-200 microg/m3) about, 8.5%, hazy periods (APC between 200-500 microg/m3), 1.4% dusty periods (APC between 500-1000 microg/m3) and about 0.7% were intense dusty periods (APC above 1000 microg/m3). Statistical analysis of the data showed significant seasonal and monthly fluctuations. The seasonal variation of the APC was further examined using different definitions of the seasons (astronomical, meteorological, and synoptic).     

Background concentrations of individual and total volatile organic compounds in residential indoor air of Schleswig-Holstein, Germany

During a monitoring campaign concentrations of volatile organic compounds (VOCs) were measured in indoor air of 79 dwellings where occupants had not complained about health problems or unpleasant odour. Parameters monitored were the individual concentration of 68 VOCs and the total concentration of all VOCs inside the room. VOCs adsorbed by Tenax TA were then analysed by means of thermal desorption, gas chromatography and mass spectrometry. The analytical procedure and quantification was done according to the recommendation of the ECA-IAQ Working Group 13 which gave a definition of the total volatile organic compound (TVOC) concentration. Using this recommendation TVOC-concentrations ranged between 33 and 1600 microg m(-3) with a median of 289 microg m(-3). Compounds found in every sample and with the highest concentrations were 2-propanol, alpha-pinene and toluene. Save for a few samples, all concentrations measured have been a factor 2 to 10 lower, compared to data from similar studies. Only a few terpenes and aldehydes were found exceeding published reference data or odour threshold concentrations. However, it has been found that sampling and analysing methods do have a considerable impact on the results, making direct comparisons of studies somewhat questionable. 47% of all samples revealed concentrations exceeding the threshold value of 300 microg TVOC m(-3) set by the German Federal Environmental Agency as a target for indoor air quality. Using the TVOC concentration as defined in the ECA-IAQ methodology is instrumental in assessing exposure to VOCs and identifying sources of VOCs. The background concentrations determined in this study can be used to discuss and interpret target values for individual and total volatile organic compounds in indoor air.     

Sampling and analytical methodology development for the determination of primary and secondary low molecular weight amines in ambient air

In this project, a sampling device and an analytical method have been developed to simultaneously analyse the most frequently found low molecular weight amines, including aliphatic, aromatic and alcohol amines. These amines are diethanolamine, ethanolamine, methylamine, isopropylamine, morpholine, dimethylamine, and aniline. A sampling device was developed using a 37 mm cassette with glass fibre filters impregnated with sulfuric acid. Immediately after sampling, the filter was transferred to vials containing a solution of dansyl chloride. Dansyl chloride was used for derivatisation because it forms aromatic sulfonamides that are fluorescent and easy to protonate for MS detection. The effect of using an internal standard made with the dansylated derivative of 1-(2-methoxyphenyl)piperazine (MOPIP) on the uncertainty and efficiency of the method was also evaluated. This internal standard was spiked directly onto filters. The coupling of HPLC/ESI-MS was used for the simultaneous analysis of all the derivatives. This method showed detection limits of about 0.03 microg mL(-1) to 0.3 microg mL(-1) of amine with an average expanded uncertainty of 3% to 6% depending on the amine. The methodology recoveries are close to 100% for all the amines, and the overall estimated expanded uncertainties vary between 10% and 13% depending on the amine. This new strategy will be useful in evaluating workplace air since a unique sampling system will be used, independent of the amine to be quantified.     

The impact of domestic wood burning on personal, indoor and outdoor levels of 1,3-butadiene, benzene, formaldehyde and acetaldehyde

The aim of this study was to quantify personal exposure and indoor levels of the suspected or known carcinogenic compounds 1,3-butadiene, benzene, formaldehyde and acetaldehyde in a small Swedish town where wood burning for space heating is common. Subjects (wood burners, n = 14), living in homes with daily use of wood-burning appliances were compared with referents (n = 10) living in the same residential area. Personal exposure and stationary measurements indoors and at an ambient site were performed with diffusive samplers for 24 h. In addition, 7 day measurements of 1,3-butadiene and benzene were performed inside and outside the homes. Wood burners had significantly higher median personal exposure to 1,3-butadiene (0.18 microg m(-3)) compared with referents (0.12 microg m(-3)), which was also reflected in the indoor levels. Significantly higher indoor levels of benzene were found in the wood-burning homes (3.0 microg m(-3)) compared with the reference homes (1.5 microg m(-3)). With regard to aldehydes, median levels obtained from personal and indoor measurements were similar although the four most extreme acetaldehyde levels were all found in wood burners. High correlations were found between personal and indoor levels for all substances (r(s) > 0.8). In a linear regression model, type of wood-burning appliance, burning time and number of wood replenishments were significant factors for indoor levels of 1,3-butadiene. Domestic wood burning seems to increase personal exposure to 1,3-butadiene as well as indoor levels of 1,3-butadiene and benzene and possibly also acetaldehyde. The cancer risk from these compounds at exposure to wood smoke is, however, estimated to be low in developed countries.     

Exposure to airborne isocyanates and other thermal degradation products at polyurethane-processing workplaces

The thermal degradation products of polyurethanes (PURs) and exposure to isocyanates were studied by stationary and personal measurements in five different occupational environments. Isocyanates were collected on glass fibre filters impregnated with 1-(2-methoxyphenyl)piperazine (2MP) and in impingers containing n-dibutylamine (DBA) in toluene. connected to a glass fibre postfilter. The derivatives formed were analysed by liquid chromatography: 2MP derivatives with UV and electrochemical detection and DBA derivatives with mass spectrometric detection. The release of aldehydes and other volatile organic compounds into the air was also studied. In a comparison of the two sampling methods, the 2MP method yielded about 20% lower concentrations for 4,4'-methylenediphenyl diisocyanate (MDI) than did the DBA method. In car repair shops, the median concentration of diisocyanates (given as NCO groups) in the breathing zone was 1.1 microg NCO m(-3) during grinding and 0.3 microg NCO m(-3) during welding, with highest concentrations of 1.7 and 16 pg NCO m(-3), respectively. High concentrations of MDI, up to 25 and 19 microg NCO m(-3), respectively, were also measured in the breathing zone during welding of district heating pipes and turning of a PUR-coated metal cylinder. During installation of PUR-coated floor covering, small amounts of aliphatic diisocyanates were detected in the air. A small-molecular monoisocyanate, methyl isocyanate, and isocyanic acid were detected only during welding and turning operations. The diisocyanate concentrations were in general higher near the emission source than in the workers' breathing zone. A sampling strategy to evaluate the risk of exposure to isocyanates is presented.     

A multiresidue method for the analysis of phenols and nitrophenols in the atmosphere

A method using GC-MS and derivatization with N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) was developed for the analysis of 20 phenolic compounds in atmospheric samples (gas and particles). Air sampling was carried out using a Hi-Vol sampler with glass fibre filter and XAD-2 resin at a flow rate of 60 m(3) h(-1). The particle and gas phases were collected separately over a period of 4 h. Samples were Soxhlet extracted, evaporated to dryness under nitrogen and refilled with acetonitrile. 100 microl of these extracts were derivatized with 100 microl of MTBSTFA at 80 degrees C for 1 h under strong stirring. Phenolic compounds were injected into a GC-MS in splitless mode and quantified as their TBDMS derivatives in the SIM mode. Mass spectral analysis of the derivatives of the 20 compounds studied indicates that the spectra are highly specific showing an ion at [M - 57]+ which is useful for structure confirmation or analysis at low levels using selected ion monitoring. Quantification limits varied between 5 microg l(-1) and 10 microg l(-1) which correspond to 20 pg m(-3) and 40 pg m(-3) for 250 m(3) of air sampled. This method was successfully applied to atmospheric samples.     

Flux of organic compounds from grass measured by relaxed eddy accumulation technique

Fluxes of some Volatile Organic Compounds (VOC) from grass were measured at a golf course in western Sweden, using the Relaxed Eddy Accumulation (REA) technique. The sampling was done by collecting VOC onto adsorbent tubes and the analysis was performed by thermal desorption followed by GC/MS. High emissions were observed after cutting. Transient fluxes of (Z)-3-hexenyl acetate (0.51 microg m(-2) s(-1)), (Z)-3-hexen-1-ol (0.14 microg m(-2) s(-1)) and (Z)-3-hexenal (0.40 microg m(-2) s(-1)) were measured, even at low temperatures. The REA technique requires a relatively large fetch area that is sometimes not available. Therefore, a procedure for correcting measured fluxes from a limited fetch is suggested.     

Development of a diffusive sampling method for determination of methyl isocyanate in air

A diffusive sampling method for determination of methyl isocyanate in air has been developed. A glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine in a commercially available diffusive sampling device was used to collect methyl isocyanate and the derivative formed was analysed with LC-MS/MS. The sampling rate was determined to be 15.6 ml min(-1), with a relative standard deviation of 7.3%. The sampler was validated for sampling periods from 15 min to 8 h, for relative humidities from 20% to 80% and for concentrations from I to 46 microg m(-3). A field validation was also made and the diffusive sampling results showed no difference compared to a pumped reference method. The impregnated filters have to be stored apart from the diffusive sampler housing and loaded into the sampler prior to each sampling.     

Emissions of reduced sulphur compounds from the surface of primary and secondary wastewater clarifiers at a Kraft Mill

Emissions of reduced sulphur compounds (RSCs) from the primary and secondary clarifiers at a Kraft mill were measured for respectively 8 and 22 days using a floating flux chamber. In the primary clarifier, dimethyl disulphide (DMDS) had the highest mean flux (0.83 microg s(-1) m(-2)) among all RSCs, and the mean flux of total reduced sulphur (TRS) was 1.53 microg s(-1) m(-2). At the secondary clarifier, dimethyl sulphide (DMS) had the highest mean flux (0.024 microg s(-1) m(-2)), and the mean flux of total reduced sulphur (TRS) was 0.025 microg s(-1) m(-2). Large variations in fluxes as a function of sampling date were observed in both clarifiers. Emission fluxes of DMS from the secondary clarifier were correlated with temperature in the flux chamber and with the biological and chemical oxygen demands (BOD and COD) of the wastewater. Emission rates of RSCs from the clarifiers were found to be insignificant by comparison with other mill sources.     

Indoor air pollution by 2-ethyl-1-hexanol in non-domestic buildings in Nagoya, Japan

2-Ethyl-1-hexanol is a possibly causative chemical in sick building symptoms, although 2-ethyl-1-hexanol has received little attention as a hazardous substance in studies on indoor air pollution. Airborne 2-ethyl-1-hexanol concentrations were measured from 2002 to 2004 in 99 rooms of 42 non-domestic buildings in Nagoya, Japan. The diffusive sampling method is effective for the measurement of a low level of 2-ethyl-1-hexanol in indoor air. The geometric mean (geometric standard deviation) of 2-ethyl-1-hexanol concentrations was 16.5 (5.4) microg m(-3) in indoor air and 1.9 (2.2) microg m(-3) in outdoor air. The maximum concentration of 2-ethyl-1-hexanol in indoor air and outdoor air was 2709 microg m(-3) and 12.4 microg m(-3), respectively. Fewer rooms in a small number of new buildings showed high concentrations of 2-ethyl-1-hexanol, while low concentrations were observed in many rooms of these buildings as well as the other new buildings. The room-to-room concentrations of 2-ethyl-1-hexanol in each building exhibited a wide variation. The geometric mean of the 2-ethyl-1-hexanol concentrations was significantly higher for indoor air than for outdoor air (p < 0.01). The correlation of the 2-ethyl-1-hexanol concentrations between indoor and outdoor air was not significant. Mechanical ventilation was effective in the temporary reduction of indoor 2-ethyl-1-hexanol level. These results suggest that the predominant source of 2-ethyl-1-hexanol was indoor areas.     

测量土壤中多溴联苯和多溴联苯醚含量不确定度评定

通过对气相色谱-质谱联用法测定土壤中多溴联苯和多溴联苯醚类化合物含量的不确定度进行评定,分析了测量过程中引入的不确定度来源,求出各不确定度分量,最后合成标准不确定度并计算相对扩展不确定度。结果表明,各化合物最大的不确定度分量是方法回收率,约占50%~90%,方法相对扩展不确定度为0.12~0.20。     

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.     

Pesticide vapours in confined atmospheres. Determination of dichlorvos by SPME-GC-MS at the microg m(-3) level

A method based on SPME is described for assessing the gaseous dichlorvos concentration in confined atmospheres like a greenhouse after a pesticide application. Sampling was made by using SPME with PDMS fibres immersed into a 250 mL sampling flask into which air samples were dynamically pumped from the analysed atmosphere. Sampling duration was 40 min and samples were then analysed by GC-MS. Calibration was performed from a vapour saturated air sample and gas phase diluted samples, and this procedure afforded a curve with a regression coefficient (R2) higher than 0.98. The repeatability of these measurements was observed with an RSD of 2.5%. This analysis procedure was then applied for the determination of gaseous dichlorvos concentrations versus time, in the atmosphere of an experimental 8 m2 and 20 m3 greenhouse. The pesticide was sprayed according to real cultivation conditions and measurements were made from 2 up to 74 h after application affording observed concentrations in the range of decades and hundreds of microg m(-3) (corresponding limits of detection and quantification were found at the level of a few microg m(-3)).     

Effect of fertilizer application on ammonia emission and concentration levels of ammonium, nitrate, and nitrite ions in a rice field

The concentrations of ammonium NH4+, nitrate NO3-, and nitrite NO2- ions were recorded along with ammonia (NH(3)) emission from a fertilized rice field located in the Kwangju province in South Korea over a period of 4 months (June to October 2006). The highest magnitude of NH(3) flux was 20,754 microg m(-2) h(-1), while the average flux value over the entire sampling period was 2,395 microg m(-2) h(-1). The highest ionic concentrations were 1.67, 0.44, and 0.71 ppm for NH4+, NO3-, and NO2- ions, respectively. Possible effects of soil pH on NH(3) fluxes were detected, as they concurrently exhibited a gradual and periodic change during the sampling period. Positive correlations existed between concentrations of NH4+ and NO2- ions and the soil pH. Positive correlations also existed between NH(3) emission flux and ambient (and water) temperatures. Results indicated that fertilizer application to rice can lead to significant emission of NH(3) along with NH4+ and NO3- ions.     

Submicrometer elemental carbon as a selective measure of diesel particulate matter in coal mines

A monitoring method for diesel particulate matter was published as Method 5040 by the National Institute for Occupational Safety and Health (NIOSH). Organic and elemental carbon are determined by the method, but elemental carbon (EC) is a better exposure measure. The US Mine Safety and Health Administration (MSHA) proposed use of NIOSH 5040 for compliance determinations in metal and nonmetal mines. MSHA also published a rulemaking for coal mines, but no exposure standard was provided. A standard based on particulate carbon is not considered practical because of coal dust interference. Interference may not be a problem if an appropriate size-selective sampler and EC exposure standard are employed. Submicrometer dust concentrations found in previous surveys of nondieselized, underground coal mines were relatively low. If a large fraction of the submicrometer dust is organic and mineral matter, submicrometer EC concentrations would be much lower than submicrometer mass concentrations. Laboratory and field results reported herein indicate the amount of EC contributed by submicrometer coal dust is minor. In a laboratory test, a submicrometer EC concentration of 31 microg m(-3) was found when sampling a respirable coal dust concentration over three times the US compliance limit (2 mg m(-3)). Laboratory results are consistent with surveys of nondieselized coal mines, where EC results ranged from below the method limit of detection to 18 microg m(-3) when size-selective samplers were used to collect dust fractions having particle diameters below 1.5 microm-submicrometer EC concentrations were approximate 7 microg m(-3). In dieselized mines, submicrometer EC concentrations are much higher.     

Validation of a diffusive sampler for NO2

A diffusive sampler for NO2, Willems badge, was validated in laboratory experiments and field tests. The collecting reagent for NO2 in the sampler is triethanolamine, and the analysis is based on a modified colorimetric method, the Saltzman method. The analysis was performed by a flow injection analysis (FIA) technique. The sampling rate for the sampler was determined to be 40.0 ml min-1. There was no effect of NO2 concentration or relative humidity on sampling rate, and the influence of sampling time was found to be small. The detection limit was 4 micrograms m-3 for a 24 h sample. The capacity is high enough to allow sampling of 150 micrograms m-3 for 7 days, which is twice the recommended Swedish short-term (24 h) guideline value as a 98-percentile over 6 months. In field tests, the sampler performed well, even at wind speeds higher than 2 m s-1, and at low temperatures. The overall uncertainty of the method was 24%. The sensitivity and capacity of the method also make it suitable for personal sampling for 2-8 h in working environments.