Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

Design and field application of an automated cartridge sampler for VOC concentration and flux measurements

One of the major limitations in advancing the understanding of tropospheric ozone and aerosol generation and developing strategies for their control is the technical ability to accurately measure volatile organic compounds (VOCs). This paper describes the design of a constant flow VOC sampler. The versatile sampler can be used for fully automated concentration and flux measurements of VOCs. The sampler incorporates a microprocessor control unit and provides highly accurate mass flow control and significant ease of operation. Sampling sequences can be programmed directly or by remote control through a PC. All important operational parameters necessary for a complete sampling audit trail are logged. Compact weatherproof housings and low power consumption allow operation at remote sites and locations which are sensitive to disturbances or have restricted access. Inner wetted surfaces of the sampler are constructed from non-contaminating materials that do not sorb or emit VOC, and thus permit the collection of representative samples even in environments with very low VOC concentrations. The cartridge magazine provides a maximum of 20 sequential cartridge samples, which allows for long-term air quality assessments. In the dual channel mode, two samples can be collected simultaneously through two independent sample loops, providing ten sequential sample pairs. This design allows the parallel collection of (a) quality assurance backup samples, (b) samples on two different types of cartridges/sorbents to allow a variety of analyses, or (c) differential samples for flux measurements using enclosure, aerodynamic profile, or relaxed eddy accumulation (REA) methods. Field applications including airplane profile measurements above a tropical rainforest area, as well as gradient and REA measurements over a mid-latitude mixed forest stand are described, and demonstrate the validity and flexibility of the system. In particular, the application of the VOC sampler as an integrated part of a REA system is emphasized.     

Development of a sampling method for the simultaneous monitoring of straight-chain alkanes, straight-chain saturated carbonyl compounds and monoterpenes in remote areas

Studies have shown that biogenic compounds, long chain secondary compounds and long lifetime anthropogenic compounds are involved in the formation of organic aerosols in both polluted areas and remote places. This work aims at developing an active sampling method to monitor these compounds (i.e. 6 straight-chain saturated aldehydes from C6 to C11; 8 straight-chain alkanes from C9 to C16; 6 monoterpenes: α-pinene, β-pinene, camphene, limonene, α-terpinene, & γ-terpinene; and 5 aromatic compounds: toluene, ethylbenzene, meta-, para- and ortho-xylenes) in remote areas. Samples are collected onto multi-bed sorbent cartridges at 200 mL min(-1) flow rate, using the automatic sampler SyPAC (TERA-Environnement, Crolles, France). No breakthrough was observed for sampling volumes up to 120 L (standard mixture at ambient temperature, with a relative humidity of 75%). As ozone has been shown to alter the samples (losses of 90% of aldehydes and up to 95% of terpenes were observed), the addition of a conditioned manganese dioxide (MnO(2)) scrubber to the system has been validated (full recovery of the affected compounds for a standard mixture at 50% relative humidity--RH). Samples are first thermodesorbed and then analysed by GC/FID/MS. This method allows suitable detection limits (from 2 ppt for camphene to 13 ppt for octanal--36 L sampled), and reproducibility (from 1% for toluene to 22% for heptanal). It has been successfully used to determine the diurnal variation of the target compounds (six 3 h samples a day) during winter and summer measurement campaigns at a remote site in the south of France.     

Design and validation of a passive deposition sampler

A new, passive particle deposition air sampler, called the Einstein-Lioy Deposition Sampler (ELDS), has been developed to fill a gap in passive sampling for near-field particle emissions. The sampler can be configured in several ways: with a protective hood for outdoor sampling, without a protective hood, and as a dust plate. In addition, there is an XRF-ready option that allows for direct sampling onto a filter-mounted XRF cartridge which can be used in conjunction with all configurations. A wind tunnel was designed and constructed to test the performance of different sampler configurations using a test dust with a known particle size distribution. The sampler configurations were also tested versus each other to evaluate whether or not the protective hood would affect the collected particle size distribution. A field study was conducted to test the sampler under actual environmental conditions and to evaluate its ability to collect samples for chemical analysis. Individual experiments for each configuration demonstrated precision of the sampler. The field experiment demonstrated the ability of the sampler to both collect mass and allow for the measurement of an environmental contaminant i.e. Cr(6+). The ELDS was demonstrated to be statistically not different for Hooded and Non-Hooded models, compared to each other and the test dust; thus, it can be used indoors and outdoors in a variety of configurations to suit the user's needs.     

In situ polar organic chemical integrative sampling (POCIS) of steroidal estrogens in sewage treatment works discharge and river water

A passive sampler (the polar organic chemical integrative sampler; POCIS) was assessed for its ability to sample natural estrogens (17β-estradiol, E2; estrone, E1 and estriol, E3) and the synthetic estrogen (17α-ethynylestradiol, EE2) in the outlet of a sewage treatment works over several weeks. The performance of the POCIS was investigated and optimised in the laboratory before field deployment with high recoveries (66-99%) were achieved for all estrogens. Moreover, it was shown that POCIS does not exhibit any preferential selectivity towards any of the target compounds. The sampling rates of E1, E2 and E3 were 0.018 ± 0.009, 0.025 ± 0.014 and 0.033 ± 0.019 L d(-1), respectively. Following field deployments of 28 days in the discharge of a sewage works, POCIS was shown to enhance the sensitivity of estrogen detection, especially for E3, and provide time-weighted average (TWA) concentrations of E1, E2 and E3, ranging from undetectable to 12 ng L(-1) upstream of the outflow of a sewage treatment works, 13 to 91 ng L(-1) at the outflow and 8 to 39 ng L(-1) downstream of the outflow. This revealed that E1, E2 and E3 are not completely removed during sewage treatment, with concentrations most likely being maintained by contributions from conjugated estrogen analogues. Grab water samples showed considerable variation in the concentrations of estrogens over a longer period (6 months). The results confirm that POCIS is an effective and non-discriminatory method for the detection of low concentrations of estrogens in the aquatic environment.     

固相萃取-超高效液相色谱-串联质谱法同时测定地表水中9种性激素

建立了地表水中9种性激素的固相萃取-超高效液相色谱-串联质谱检测方法。利用HLB固相萃取柱富集水体中痕量性激素,用甲醇洗脱并浓缩,再以1 mmol/L氟化铵-乙腈为流动相,经C_(18)柱分离,采用电喷雾离子源、质谱多反应监测模式,内标法定量,实现了地表水中9种性激素的同时检测。方法检出限为0. 1～1. 8 ng/L,在低、中、高3个加标水平下,性激素的平均回收率为69. 6%～115. 0%,相对标准偏差为3. 2%～17. 7%。该方法灵敏度高,定性准确,操作简单高效,适用于地表水中9种性激素的定性定量分析。     

Dissipation and residue of MCPA (4-chloro-2-ethylphenoxyacetate) in wheat and soil

A rapid and simple HPLC method has been developed for the quantitation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in both wheat and soil samples. Samples were extracted in acidic media and cleaned up by solid-phase extraction with C(18) cartridges before HPLC-DAD detection. The limits of detection and quantification of MCPA were 0.02 ng and 0.01 mg/kg for both wheat and soil. The mean recoveries ranged from 87.1% to 98.2%, and the RSDs ranged from 0.604% to 3.44% for the three spiked levels (0.01, 0.1, 0.5 mg/kg). The proposed method was successfully applied to the analysis of MCPA residues in wheat and soil samples from an experimental field. The dissipation half-lives in soil were calculated to be 3.22 days (Beijing) and 3.10 days (Tianjin), respectively. Direct confirmation of the analytes in real samples was achieved by gas chromatography-mass spectrometry. The results indicated that at harvest time, the residues of MCPA in wheat were well below the maximum residue levels and were safe to apply in wheat.     

Simplification and validation of a large volume polyurethane foam sampler for the analysis of persistent hydrophobic compounds in drinking water

The use of a large volume polyurethane foam (PUF) sampler was validated for rapid extraction of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in raw water and treated water from drinking water plants. To validate the recovery of target compounds in the sampling process, a (37)Cl-labeled standard was spiked into the 1st PUF plug prior to filtration. An accelerated solvent extraction method, as a pressurized liquid extractor (PLE), was optimized to extract the PUF plug. For sample preparation, tandem column chromatography (TCC) clean-up was used for rapid analysis. The recoveries of labeled compounds in the analytical method were 80-110% (n = 9). The optimized PUF-PLE-TCC method was applied in the analysis of raw water and treated potable water from seven drinking water plants in South Korea. The sample volume used was between 18 and 102 L for raw water at a flow rate of 0.4-2 L min(-1), 95 and 107 L for treated water at a flow rate of 1.5-2.2 L min(-1). Limit of quantitation (LOQ) was a function of sample volume and it decreased with increasing sample volume. The LOQ of PCDD/Fs in raw waters analyzed by this method was 3-11 times lower than that described using large-size disk-type solid phase extraction (SPE) method. The LOQ of PCDD/F congeners in raw water and treated water were 0.022-3.9 ng L(-1) and 0.018-0.74 ng L(-1), respectively. Octachlorinated dibenzo-p-dioxin (OCDD) was found in some raw water samples, while their concentrations were well below the tentative criterion set by the Japanese Environmental Ministry for drinking water. OCDD was below the LOQ in the treated drinking water.     

Assessment of sorbent impregnated PUF disks (SIPs) for long-term sampling of legacy POPs

Two field studies were conducted for one year using sorbent-impregnated polyurethane foam (SIP) disks for PCB and PBDE air sampling. SIP disks were introduced by Shoeib et al. (2008) as an alternative passive air sampling medium to the polyurethane foam (PUF) disk and have the advantage of a higher holding capacity for organic chemicals. The first study on SIP disks confirmed their application for measuring volatile perfluorinated compounds (PFCs) and their ability to maintain time-integrated (linear) air sampling. In this study, the suitability of the SIP disks for long-term sampling of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorobenzene (HCB) was assessed. SIP disks were deployed at a rural site in the UK and harvested after periods ranging from 35-350 days. Atmospheric POP concentrations were monitored with a high-volume air sampler during the deployment period. Linear uptake was observed for all monitored PCBs and PBDEs over the full exposure time. Air-sampler equilibrium was observed for HCB after 6 months. In a second field study, SIP disks were deployed for one year at 10 sites on a latitudinal transect in the UK and Norway, at which air sampling has been undertaken previously with different passive air sampling media since 1994. The estimated concentrations and spatial distributions derived from the SIP disks were largely in agreement with previously reported data.     

固相萃取气相色谱法测定水中15种硝基苯类化合物

使用Oasis HLB固相萃取柱,以正己烷/丙酮混合溶剂(体积比为3∶1)为洗脱溶剂,采用毛细管柱气相色谱电子捕获检测器同时测定水中15种硝基苯类化合物,以保留时间定性,外标标准曲线法定量。硝基苯和硝基甲苯在50.0μg/L～1 000μg/L、其他硝基苯类化合物在5.00μg/L～100μg/L范围内线性良好,检出限硝基苯和硝基甲苯为0.035μg/L～0.052μg/L,其他硝基苯类化合物为0.003 5μg/L～0.005 6μg/L,加标水样平行测定的RSD为1.4%～4.0%,平均回收率为92%～100%。     

Compact semi-automatic incident sampler for personal monitoring of volatile organic compounds in occupational air

Suddenly occurring and time limited chemical exposures caused by unintended incidents might pose a threat to many workers at various work sites. Monitoring of exposure during such occasional incidents is challenging. In this study a compact, low-weight and personal semi-automatic pumped unit for sampling of organic vapor phase compounds from occupational air during sporadic and suddenly occurring incidents has been developed, providing simple activation by the worker potentially subjected to the sudden occurring exposures when a trained occupational hygienist is not available. The sampler encompasses a tube (glass or stainless steel) containing an adsorbent material in combination with a small membrane pump, where the adsorbent is capped at both ends by gas tight solenoid valves. The sampler is operated by a conventional 9 V battery which tolerates long storage time (at least one year), and is activated by pulling a pin followed by automatic operation and subsequent closing of valves, prior to shipping to a laboratory. The adjustable sampling air flow rate and the sampling time are pre-programmed with a standard setting of 200 mL min(-1) and 30 min, respectively. The average airflow in the time interval 25-30 min compared to average airflow in the interval 2-7 min was 92-95% (n = 6), while the flow rate between-assay precisions (RSD) for six different samplers on three days each were in the range 0.5-3.7%. Incident sampler recoveries of VOCs from a generated VOC atmosphere relative to a validated standard method were between 95 and 102% (+/-4-5%). The valves that seal the sampler adsorbent during storage have been shown to prevent an external VOC atmosphere (500 mg m(-3)) to enter the adsorbent tube, in addition to that the sampler adsorbent is storable for at least one month due to absence of ingress of contaminants from internal parts. The sampler was also suitable for trapping of semi-volatile organophosphates.     

Qualitative Detection of Volatile Organic Compounds in Outdoor and Indoor Air

The present work attempts to identify VOC's in outdoor and indoor air in Mumbai City India. Ambient air was adsorbed on especially fabricated stainless steel cartridge packed with activated coconut charcoal at uniform flow rate. Qualitative identification of VOC's was done by thermally desorbing air from the cartridges and subsequent analysis on Varian GC-MS using NIST Library. The outdoor monitoring locations include residential area, commercial area, industrial, airport, petrol pumps, traffic junctions, arterial roads, highways, slums, parking area, service garages and municipal dump sites. The indoor locations comprised of air-conditioned and non air-conditioned offices, bedrooms, shops and instrumentation laboratory. The identified VOC's include aldehydes, ketones, polynuclear aromatic hydrocarbons, aromatic acids, oxygenated hydrocarbons, amines, esters and halogenated compounds. Thirteen VOCs in outdoor air and seven in indoor air amongst those identified, figure in the list of Hazardous Air Pollutants listed in Title III of the U.S. EPA Clean Air Act Amendments of 1990.     

Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

Determination of the dialdehyde glyoxal in workroom air-development of personal sampling methodology

The dialdehyde glyoxal (ethanedial) is an increasingly used industrial chemical with potential occupational health risks. This study describes the development of a personal sampling methodology for the determination of glyoxal in workroom air. Among the compounds evaluated as derivatizing agents; N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH), 1,2-phenylenediamine (OPDA), 1-dimethylaminonaphthalene-5-sulfonylhydrazine (dansylhydrazine, DNSH) and 2,4-dinitrophenylhydrazine (DNPH), DNPH was the only reagent that was suitable. Several different samplers were evaluated for sampling efficiency of glyoxal in workroom air using DNPH as derivatizing agent; in-house DNPH coated silica particles packed in two different types of glass tubes, impingers containing acidified DNPH solution, filter cassettes containing glass fibre filters coated with DNPH, a commercially available solid phase cartridge sampler originally developed for formaldehyde sampling (Waters Sep-Pak DNPH-silica cartridge), and the commercially available SKC UMEx 100 passive sampler originally developed for formaldehyde sampling. Aldehyde atmospheres for sampler evaluation were generated with an in-house made vapour atmosphere generator coupled to a sampling unit, with the possibility of parallel sampling. The resulting glyoxal-DNPH derivative was determined using both LC-UV and LC-APCI-MS with negative ionization. By far, the highest recovery of glyoxal was obtained employing one of the in-house DNPH coated silica samplers (93%, RSD = 3.6%, n = 12).     

Development of a personal monitoring method for nitrogen dioxide and sulfur dioxide with Sep-Pak C18 cartridge sampling and ion chromatographic determination

Personal monitoring methods for the determination of hourly integrated concentrations of NO2 and SO2 in ambient air have been developed. Triethanolamine (TEA)-impregnated C18 Sep-Pak cartridges were used to collect NO2 and SO2 simultaneously. After sampling, NO2 and SO2 as their nitrite, nitrate, sulfite and sulfate analogues were stripped from the cartridges with a solution of 5% methanol in distilled, deionized water (DDW) and then determined by ion chromatography. Laboratory tests were conducted to evaluate the sampling rate, collection and recovery efficiencies, breakthrough volumes, absorption capacity, interference and sample stability on the cartridge during storage. NO2 and SO2 detection limits of 0.3 and 0.4 ppb respectively for 1 h samples were obtained. Recoveries for both NO2 and SO2 exceeded 85%.     

Lead in grass in the Scottish uplands: deposition or uptake?

If it is assumed that the Pb collected in grass samples is derived mainly from atmospheric deposition then grass samples can be used as a convenient and easily analysed monitor for Pb deposition, in particular to establish the isotopic composition of current deposition in remote locations. As some studies have demonstrated a strong correlation between soil and grass Pb concentrations, it was considered important to establish the proportion of soil Pb in the grasses used to monitor atmospheric deposition at upland locations in Scotland. Consideration of earlier studies provided evidence that very little, if any, Pb in grass was derived from soil. Lead isotope analysis, by thermal ionisation mass spectrometry, of grasses grown on soils spiked with enriched (207)Pb in the field situation allowed the relative contribution of atmospheric deposition and soil to the grass Pb to be calculated. In most cases, >80% of Pb in grass was derived from atmospheric deposition and in recent years this value was >90%. Recalculation of the (206)Pb/(207)Pb ratio in grass samples showed that there was very little error in the results, published previously, which were based on the assumption that all the Pb collected with grass was derived from the atmosphere. The trends established by measuring the (206)Pb/(207)Pb ratio in grasses were confirmed and remain valid.     

加压流体萃取-气相色谱质谱法测定土壤和沉积物中27种拟除虫菊酯类农药

建立了加压流体萃取-气相色谱质谱法测定土壤和沉积物中27种拟除虫菊酯类农药的方法。以丙酮/正己烷(V∶V=1∶1)为萃取溶剂,在120℃和10. 3 MPa条件下静态萃取7 min,循环3次,石墨化炭黑串接氨丙基键合硅胶固相萃取柱净化,HP-5MS UI色谱柱分离,优化了提取和分析过程的重要条件。方法检出限为0. 001~0. 012 mg/kg,土壤中低、高浓度的加标回收率范围分别为68. 3%~123%和75. 3%~115%,沉积物中低、高浓度的加标回收率范围分别为67. 1%~120%和78. 6%~110%,单一目标物的相对标准偏差(RSD)均<20%(n=6)。实验结果表明,该方法消耗溶剂少、效率高、检出限低、精密度和准确度好,适用于土壤和沉积物中拟除虫菊酯类农药残留的测定。     

除湿机冷凝水中亚硝酸盐的浓度与大气环境质量的关系探讨

探讨了家用除湿机作为空气水溶性物质采集器的可行性。通过离子色谱仪对冷凝水离子成分的分析,并与空气总悬浮微粒(TSP)可溶性化学成分的对比,发现水汽中大部分阴阳离子的含量只比TSP低1个数量级。但TSP中一般检测不出亚硝酸根,而在水汽中则可检测出亚硝酸根离子,且水汽中亚硝酸根离子的浓度与取样位置的大气环境质量有关。     

气相色谱法测定柑橘和土壤中螺螨酯残留

以丙酮为提取剂,二氯甲烷为萃取剂,采用弗罗里硅土柱净化,气相色谱-电子捕获检测器测定柑橘和土壤中的螺螨酯残留,优化了样品前处理条件。方法在0.141μg/L～5.65 mg/L范围内线性良好,最低检出限为0.003 5 mg/kg,空白样品在0.050 mg/kg、0.500 mg/kg、1.00 mg/kg 3个添加水平上的平均回收率为82.2%～110%,平行测定的RSD为2.6%～9.8%。     

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.