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.     

Passive vapor monitoring of underground storage tanks for leak detection

Passive vapor monitoring of underground storage tanks (USTs) containing volatile hydrocarbons at locations external to the tank (an external system) is touted as a fast and effective method of leak detection. However, major gaps remain in our knowledge of the physical processes that relate a measured vapor concentration to the leak rate, thus making network design according to a quantitative design criterion nearly impossible, and differentiation between surface spills and a leaking UST requires certain levels of sophistication in the leak detection system and in the analysis that are not usually available. Heavier-than-air vapors from the constituents of stored hydrocarbons could result in a density-driven convective propagation component that complicates the design of leak detection systems, and finally, detection times are highly sensitive to concentration detection threshold levels set by the system. The use of inadequate systems and analyses can lead to either wasted efforts or excessive subsurface contamination. This paper discusses the physical processes involved, explores the above aspects of external passive vapor leak detection design, and suggests some alternatives as they pertain to gasoline service stations.     

食品企业周边空气中异味挥发性有机物测定方法比较

以1个典型食品生产企业(酱菜厂)周边的异味挥发性有机物监测为例,介绍了罐采样-GC/MS、便携式GC/MS、SPME-GC/MS以及SPME-异味分析系统等4种监测方法的实际应用,从定性、定量监测结果等方面,比较了4种监测方法的特点。罐采样-GC/MS、便携式GC-MS 2种方法适用于定性、定量检测,在有标准样品的前提下,定量结果总体可比;SPME-GC/MS以及SPME-异味分析系统2种方法更适用于定性检测。     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

典型废酸油渣中54种VOCs和16种P AHs的分布特征研究

通过运用GC-MS方法对3家润滑油生产企业废酸油渣中的54种挥发性有机物(VOCs)和16种多环芳烃(PAHs)进行定性及定量分析.结果表明,54种VOCs有12种被检出,检出率为22.2％,其中1,2,4-三甲苯在75个样品中均有检出,检出率为100％.54种VOCs质量分数为ND～12.5 mg/kg,其中质量分数...     

Indoor air sampling of organophosphate triesters using solid phase extraction (SPE) adsorbents

In this paper we demonstrate the use of SPE cartridges for sampling of organophosphate triesters in indoor air by adsorptive enrichment. The method has been optimised for the sampling and analysis of organophosphate triesters using a 25 mg aminopropyl silica SPE cartridge. The same cartridge is used for the active air sampling as well as for the subsequent extraction and clean-up of the sample. This makes the method fast and eliminates some tedious and time-consuming manual sample handling steps. Sampling and extraction efficiency was high for the investigated organophosphates, and limit of detection was in the range 0.1-0.3 ng m(-3). The method was applied to measurements of organophosphate triesters in two lecture halls and an electronics dismantling facility, and was compared with results from common filter/adsorbent sampling at each site. Analysis was made by GC with selective detection by NPD set in phosphorus mode, and by GC-MS. Thirteen organophosphate triesters (not counting isomers) were detected in the electronic dismantling facility. Chlorinated organophosphate triesters were detected in all locations with concentrations over 1 microg m(-3) in the lecture halls. This kind of adsorptive enrichment using an SPE cartridge could be adjusted to other types of analytes as well.     

植物油烟组分的色质联机分析

将植物油烟采集在玻璃纤维滤筒中 ,用环己烷处理样品 ,样品经过净化处理 ,然后进行色质联机分析。对油烟化学成分的分析有助于人们研究油烟对人体健康的影响     

A ten channel fibre-optic device for distributed sensing of underground hydrocarbon leakage

With millions of fuel storage tanks and oil pipelines installed around the world, there is inevitably frequent leakage of potentially hazardous hydrocarbons. As many of these installations are below ground, it can often be many years before the extent of the leak is discovered. We have previously reported the development of a sensor for the detection of such subterranean leaks, using infrared reflectometry to interrogate a hydrocarbon sensitive membrane. However, a single sensor cannot provide any information about the flow rate or direction of the leak. This paper describes the extension of the technology to a multi-channel distributed sensing system, using optical fibres capable of distributing the sensors over large subterranean areas. Results are reported from the evaluation of the device, which consisted of monitoring the movement of different hydrocarbons (gasoline, diesel and insulating oil) through a vertical sand-filled vessel.     

The determination of carbonyl compounds in air using a robotic sampling preparation system integrated to a gas chromatograph with a nitrogen-phosphorus detector

A totally automated solid phase extraction gas chromatography procedure was developed for the sampling and analysis of carbonyl compounds in air. In this system, two PrepStation modules were used, one for the preparation and elution of 2,4-dinitrophenylhydrazine silica cartridges, and the other for air sampling. The sample collected by the sampling module was eluted to an autosampler vial in the PrepStation module and then transferred to the gas chromatograph for analysis via a robotic arm. The sampling module was modified to enable air sampling via an external pump. A typical run by this technique required 142 min, 100 min for air sampling and 42 min for the other operations, including a GC analysis time of 25 min. Recoveries of at least 85% were obtained for all compounds studied. The detection limits for formaldehyde, acetaldehyde and acetone were 2.2, 2.7 and 2.2 ppbv, respectively. All operations, including the conditioning of the cartridges, were performed without any intervention from the analyst.     

A Study of Sorptive Loss Patterns for Reduced Sulfur Compounds in the Use of the Bag Sampling Method

In this work, the basic properties of the bag sampling method were examined and characterized in terms of recovery rate with respect to four reduced sulfur compounds (RSC) including H₂S, CH₃SH, DMS, and DMDS. For this comparative study, two types of calibration approaches were performed to evaluate the relative RSC loss due to bag sampling. As a reference calibration tool, a syringe dilution (SD) method was applied. The working standards prepared by diluting the primary standard in a gas-tight syringe (as a mixing chamber) were injected to the GC/PFPD through a loop-injection system to yield a background calibration information. In contrast, the target calibration was performed based on a bag dilution (BD) method. To this end, working standards for multiple calibration points were prepared by two different bag types (Tedlar bag (TB) and polyester bag (PB)). These standards were then drawn by the same syringe and injected into the GC/PFPD via loop. On the basis of these comparative analyses, both absolute and relative differences in RSC recovery rates (RR) were evaluated (e.g., comparison of wall-loss effect). The results indicate that TB has a mean RR of 87% for the four RSC with their values ranging from 82 (CH₃SH) to 91% (DMDS). On the other hand, the results of PB generally exhibited slightly reduced RR with their mean values of 77% (range: 73% of H₂S to 83% of DMS). The results of this study generally suggest that the losses of RSC samples, while inevitable with the bag sampling method, exhibit certain patterns between different RSCs and between different grab sampling materials.     

气相色谱-质谱法测定大气中98种挥发性有机物

通过色谱-质谱联用法(简称GC-MS),利用低温冷阱技术对大气中的VOCs进行浓缩富集,然后经过加热解吸分别至毛细管色谱柱和FID检测器及MS检测器,对大气中98种挥发性有机化合物(VOCs)进行分离、定性、定量测定。方法检出限为0.008×10-9~0.100×10-9(V/V);线性相关系数的平方值为0.992 7~1,相对标准偏差为4.0%~20.2%,总体标准偏差为0.154 2~0.952 1。     

Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

Beach geomorphic factors for the persistence of subsurface oil from the Exxon Valdez spill in Alaska

Oil from the 1989 Exxon Valdez oil spill persists in some of the Prince William Sound (Alaska) beaches and continues to be a potential threat to the fauna. This paper reports a field investigation during the summer of 2008 of groundwater flow and solute transport in a tidal gravel beach in Smith Island, Prince William Sound. The beach contains oil on one side, the left side (facing landward). Field measurements of water table, salinity, and tracer (lithium) concentration were obtained for an approximate duration of 64 h for two transects, the oiled transect and a clean transect (the right transect). It was found that the hydraulic conductivity and the fresh groundwater recharge into the two transects were similar. It was also found that the beach slope of the mid to high tidal zone along the oiled (left) transect was ~7.4% which is considerably smaller than that of the clean (right) transect (~11.8%). This suggests a higher flushing/replenishing of the right transect with nutrients and/or oxygen, which would have enhanced biodegradation of oil on the right transect if that oil was not washed by waves. We also found that the degree of oiling at each location was inversely dependent on the armoring of the beach surface with clasts and boulders. The applied tracer concentration at the left transect was less than 2% of the source or close to the background level at all locations except a seaward well closest to the applied location, indicating that the tracer applied was diluted or washed out from the beach during the application. Thus, in situations where oil biodegradation is limited by the availability of nutrients and/or dissolved oxygen, applying the chemicals on the beach surface would most likely not enhance oil biodegradation as the applied chemicals would be greatly diluted prior to reaching the oil. Thus, deep injection of nutrients and/or dissolved oxygen is probably the only option for enhancing oil biodegradation.     

Application of portable gas chromatography-photo ionization detector combined with headspace sampling for field analysis of benzene, toluene, ethylbenzene, and xylene in soils

A method based on headspace (HS) sampling coupling with portable gas chromatography (GC) with photo ionization detector (PID) was developed for rapid determination of benzene, toluene, ethylbenzene, and xylenes (BTEX) in soils. Optimal conditions for HS gas sampling procedure were determined, and the influence of soil organic matter on the recovery of BTEX from soil was investigated using five representative Chinese soils. The results showed that the HS-portable-GC-PID method could be effectively operated at ambient temperature, and the addition of 15 ml of saturated NaCl solution in a 40-ml sampling vial and 60 s of shaking time for sample solution were optimum for the HS gas sampling procedure. The recoveries of each BTEX in soils ranged from 87.2 to 105.1 %, with relative standard deviations varying from 5.3 to 7.8 %. Good linearity was obtained for all BTEX compounds, and the detection limits were in the 0.1 to 0.8 μg kg^?1 range. Soil organic matter was identified as one of the principal elements that affect the HS gas sampling of BTEX in soils. The HS-portable-GC-PID method was successfully applied for field determination of benzene and toluene in soils of a former chemical plant in Jilin City, northeast China. Considering its satisfactory repeatability and reproducibility and particular suitability to be operated in ambient environment, HS sampling coupling with portable GC-PID is, therefore, recommended to be a suitable screening tool for rapid on-site determination of BTEX in soils.     

Comparison of 24 h averaged VOC monitoring results for residential indoor and outdoor air using Carbopack X-filled diffusive samplers and active sampling--a pilot study

Analytical results obtained by thermal desorption GC/MS for 24 h diffusive sampling of 11 volatile organic compounds (VOCs) are compared with results of time-averaged active sampling at a known constant flow rate. Air samples were collected with co-located duplicate diffusive sampling tubes and one passivated canister. A total of eight multiple-component sampling events took place at fixed positions inside and outside three private homes. Subsequently, a known amount of sample air was transferred from the canister to an adsorbent tube for analysis by thermal desorption GC/MS. Results for the 11 most prevalent compounds--Freon 11, 1,3-butadiene, benzene, toluene, tetrachloroethene, ethylbenzene, m,p-xylene, o-xylene, 4-ethyltoluene, 1,3,5-trimethylbenzene, and p-dichlorobenzene--show that the ratio of average study values (diffusive sampling to active sampling) is 0.92 with 0.70 and 1.14 extreme ratios. Absolute percent difference for duplicate samples using diffusive sampling was <10% for the four most prevalent compounds. Agreement between the two sampling approaches indicates that the prediction of approximately constant diffusive sampling rates based on previous laboratory studies is valid under the field conditions.     

直接进样-热脱附-GC-MS快速测定大气细颗粒物中有机示踪物

建立了直接进样-热脱附-GC-MS快速测定细颗粒物中甾烷类和藿烷类有机示踪物的方法。经实验条件优化,13种目标化合物的线性回归方程的相关系数均在0.990以上,空白加标回收率为81.4%~102.3%,实际样品加标回收率为79.1%~112.9%,相对标准偏差小于13.2%。当采样体积为24 m~3时,各目标化合物的检出限为0.008~0.084 ng/m~3,方法灵敏度高。利用该方法测定了北京城区采暖季和非采暖季PM2.5实际样品,结果表明:各目标物均有检出,且采暖季的甾烷类和藿烷类化合物的总量均明显高于非采暖季。该方法无需复杂的前处理和有机溶剂,操作简便快捷,在颗粒物中非极性化合物的快速检测方面具有很大的应用价值。     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

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

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

DNPH衍生化采样-溶剂解析-高效液相色谱法同时测定木制品中25种醛酮化合物

建立了DNPH衍生化采样-溶剂解析-高效液相色谱测定木制品中醛酮化合物的方法。采样时需在2,4-二硝基苯肼吸附管前串联一只SEP-PAK脱臭氧小柱;采样体积应≤10 L,流量≤400 m L/min。该法对25种醛(酮)化合物对应的衍生物分离效果良好,在0.005~3 mg/L范围内线性良好,相关系数R2≥0.999 6,回收率为85.3%~113.5%,精密度为2.67%~4.56%。采样量为10 L时,25种醛(酮)化合物的检出限和定量限分别≤0.16和0.50μg/m3。     

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.