Artifact evidence in carbonyl compound sampling using the enclosure technique with cuvette system

Biogenic hydrocarbon emission rates from individual plant species have been estimated experimentally placing small plants or branches in enclosures and measuring the emission rates of the compounds. All-Teflon chambers (cuvettes) where air samples are drawn through tubes packed with adsorbents, have been commonly used for plant enclosure. Sampling of carbonyl compounds emitted from plants has been done using 2,4-dinitrophenylhydrazine coated particles and the derivative carbonyl compounds have been analyzed by HPLC-UV. In this work, the enclosure technique using a cuvette for measurements of carbonyl compound emissions from plants was evaluated. Blank measurements in an empty cuvette have revealed quite different results for experiments performed under laboratory and field conditions. Rigorous univariate statistical analysis of the data obtained indicate that the analytical procedure to determine carbonyl compounds at trace levels in emission samples using the cuvette may lead to positive artifacts during field sampling. This analysis applied to laboratory measurements showed no difference in the results for the cuvette and external lines. Multivariate statistical calculations point out that solar light intensity accounts for the high carbonyl compound levels, especially for acetaldehyde, in the empty cuvette.     

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.     

An evaluation of a fast sampling procedure for the trace analysis of volatile organic compounds in ambient air

This study deals with the evaluation of a fast method for sampling of volatile organic compounds in ambient air. Special bags made of an inert material are used together with a large handpump which allows a sampling of one liter per second. After the sampling, the pollutants are concentrated by adsorption on Tenax and transfered by heat desorption, to a small capillary precolumn cooled with liquid nitrogen, or directly trapped on the precolumn. The suitability of this technique was evaluated by sampling complex synthetic mixtures of known concentration and composition, after which the samples were submitted to a series of operations such as transport, aging, changing of the humidity, heating and cooling, irradiation, etc. Changes in the original mixtures, caused by adsorption, diffusion, chemical or photochemical reactions were investigated by GC-MS analysis. The results of the study show that under certain conditions the samples can be preserved for a rather long period of time without noticeable changes in composition. However for certain compounds, severe quantitative losses occur after one day storage. Finally a practical application of this method is described in a recent case of strong odour annoyance by a chemical plant in the north of Belgium.     

Colorimetric determination of formaldehyde in air using a hanging drop of chromotropic acid

A simple and sensitive method to determine parts per billion (ppb) of atmospheric formaldehyde in situ, using chromotropic acid, is described. A colorimetric sensor, coupled to a droplet of 15.5 microL chromotropic acid, was constructed and used to sample and quantify formaldehyde. The sensor was set up with two optical fibers, a light emitting diode (LED) and two photodiodes. The reference and transmitted light were measured by a photodetection arrangement that converts the signals into units of absorbance. Air was sampled around the chromotropic acid droplet. A purple product was formed and measured after the sampling terminated (typically 7 min). The response is proportional to the sampling period, analyte concentration and sample flow rate. The detection limit is approximately 2 ppb and can be improved by using longer sampling times and/or a sampling flow rate higher than that used in this work, 200 mL min-1. The present technique affords a simple, inexpensive near real-time measurement with very little reagent consumption. The method is selective and highly sensitive. This sensor could be used either for outdoor or indoor atmospheres.     

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.     

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.     

A diffusive sampling device for the determination of formaldehyde in air using N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) as reagent

A new method utilizing the diffusive sampling of formaldehyde in air has been developed. Formaldehyde is sampled with the use of a glass fiber filter impregnated with N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) and phosphoric acid. The formaldehyde hydrazone formed is desorbed from the filter with acetonitrile and determined by high-performance liquid chromatography (HPLC) with UV/visible detection at 474 nm. The sampling rate was determined to be 24.7 mL min-1 with a relative standard deviation of 7% for 48 experiments. The measured sampling rates were not dependent on the formaldehyde concentration (0.1-1.0 mg m-3), sampling time (15-482 min) or relative humidity (20-85%). The detection limit was 70 micrograms m-3 for a 15 min sampling period and 2 micrograms m-3 for an 8 h sampling period.     

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.     

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.     

Determination of 14 amines in air samples using midget impingers sampling followed by analysis with ion chromatography in tandem with mass spectrometry

An Ion Chromatography-Mass Spectrometry (IC-MS) method was developed for the simultaneous quantification of 14 volatile amines in air. The method includes collection of compounds into two midget impingers in a row filled with 15 ml of ultrapure water. The analytical performances with mass spectrometry detection were compared to those obtained with classical conductivity detection. The use of mass spectrometry detection (in SIM mode) overcomes most of the coelutions encountered with conductivity detection. Although the linearity domain of calibrations is reduced for the MS detection as compared with the CD detection, the detection limits in MS detection are highly lowered allowing the quantification of amines at the levels of μg m(-3) in air with a good accuracy for most compounds (RSD of less than 10%). This method was successfully applied to the analysis of amines released from polyurethane foams. Seven amines were identified and some in high concentrations, like dimethylaminoethanol, NIAX and TEDA.     

某乡镇大气中毒害挥发性有机物的研究

对经济较发达的某乡镇大气的毒害挥发性有机化合物研究表明,该镇城区及其较发达的乡村已受到一定程度的有机污染,大气中主要存在苯系物、萘、氯代烃等毒害挥发性有机化合物.个别样品的苯乙烯含量高达14.50μg/m3,此值已超过中国居住区最高容许浓度.     

Erroneous mass transit system and its tended relationship with motor vehicular air pollution (An integrated approach for reduction of urban air pollution in Lahore)

Air pollution is threat to the lives of people living in big cities of Pakistan. In Lahore 1,250 people die annually because of air pollution.Mass transit system that can be put forth as solution to urban air pollution is contingent with right choice of system and its affiliation with motorized vehicles and nature of urban air pollution.Existing mass transit system in Lahore due to untrue operation causes surfeit discharge of motor vehicular carbon monoxide. Tended relationships of mass transit system with motorized vehicles and urban air pollution are quite noteworthy. The growing motor vehicles (a consequence of flawed public mass transit system) are potential source of urban air pollution. This paper attempts to highlight correlations and regression curves of existing mass transit system. Further it recommends a two facet approach for reduction of motor vehicular air pollution in Lahore.     

Passive sampling in combination with thermal desorption and gas chromatography as a tool for self-assessment of chemical exposure

Diffusive samplers for monitoring of air quality are user-friendly devices that can normally be operated by the user himself. Hence these samplers are suitable for self-assessment. Practical and work organisational aspects of self-assessment of chemical exposure were studied in different occupational settings. It was found that the diffusive sampler used in these studies, the Perkin-Elmer tube in combination with thermal desorption, worked well for the purpose and could be correctly handled by the individuals using it. The results from self-assessments agreed well with expert measurements carried out by an occupational hygienist. However, in order to obtain a sustainable system of self-assessment strong organizational support is needed.     

The use of semipermeable membrane devices as passive samplers to determine persistent organic compounds in indoor air

In the study reported here semipermeable membrane devices (SPMDs) were used to sample 28 PAHs and 19 PCBs in the gas phase in 15 single-family houses located in an area where domestic wood burning is widespread. Eight of the households used wood burning appliances whereas the others used other systems for residential heating. Most of the studied compounds were found in the houses: the PAHs at levels that were similar to or slightly higher than published SPMD-sampled levels for background or urban sites in Sweden, and the PCBs at levels that were somewhat lower than those recently found in both indoor and outdoor urban locations. A principal component analysis revealed that wood-burning heating systems may contribute to PAHs in indoor air. The sources may be emissions indoors or penetration from outdoors. The convenience of SPMD technology facilitates its use for semi-quantitative screening and monitoring of various persistent organic compounds indoors in dwellings and working environments.     

On-site simultaneous determination of anions and cations in drainage water using a flow injection-capillary electrophoresis system with contactless conductivity detection

Drainage water diverted from a farm pasture, which was heavily loaded with manure, was monitored during a rain event. Concurrent anion and cation determinations at intervals of 10 min could be achieved with a new capillary electrophoresis system employing dual injection at opposite ends of the separation capillary. The flow injection approach enabled automation of the sampling process. Interruption of the separation voltage was not necessary. Contactless conductivity detection with an electrolyte solution optimized for the purpose allowed the facile simultaneous detection of the inorganic ions Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), NO(2)(-), NH(4)(+), K(+), Ca(2+), Na(+) and Mg(2+) and the acquisition of temporal concentration profiles of these species. The detection limits achieved were between 20 and 200 [micro sign]g l(-1) for all ions and the repeatability of peak areas and peak heights was better than 1%. The quantitative results were verified by analysing individual samples later in the laboratory with photometry and ion chromatography and the average deviations were found to be between 4 and 12%. This contribution presents a further step in the development of capillary electrophoresis towards a fully automated, low maintenance field method.     

Turbidimetric determination of chloride in different types of water using a single sequential injection analysis system

A sequential injection analysis system for the turbidimetric determination of chloride in different types of water is proposed. The determination is based on the reaction of chloride with silver ions and the subsequent measurement of the turbidity caused by silver chloride precipitation. In this method, the use of toxic reagents, such as mercury thiocyanate, commonly employed in most spectrophotometric techniques for chloride determination, is avoided. The main feature of the developed system is the use of a single configuration to carry out the determination over a wide concentration range (2-400 mg L(-1)) by changing only the aspirated sample volume. This characteristic allows the determination of chloride in ground, surface and wastewaters using the same manifold. In addition, a considerable saving of precipitating reagent is achieved due to non-continuous consumption. The results obtained with the developed system were statistically indistinguishable from those of the potentiometric titration reference method. Relative standard deviations for ten consecutive injections were lower than 3.7%, with a sampling frequency of between 55 and 57 determinations per hour.     

The design of long-term air quality monitoring networks in urban areas using a spatiotemporal approach

The implementation and maintenance of an air pollution monitoring program can be expensive and time consuming, especially when the aim is for long-term monitoring over a significant area. Consequently, it is essential that sites are optimized to provide the best representative cover while minimizing costs. In the past, there has been a tendency to locate sampling stations at pollution hot-spots. While this is acceptable for determining a maximum potential exposure or identifying the extent of a risk, there are limitations to this approach when assessing the potential impact of any future abatement strategies or determining the level of exposure outside the vicinity. This paper presents an approach in which representative air quality assessments can be undertaken for an urban area using the minimum number of measurement sites. A novel methodology is described that involves site selection to capture the maximum variance in measured pollutants, while minimizing spatiotemporal autocorrelation between the selected sites. A case study is presented for Yazd, Iran. Overall, the results show that the proposed methodology can be effective and enable the long-term monitoring of air pollution to be undertaken on a cost-effective basis in urban areas. In addition, there is the potential for the methodology to be utilized for other forms of pollution (e.g., water, soil, and noise).     

The determination of ambient formaldehyde using a dual coil system and an assessment of dominant factors that influence its abundance in Korea

An enhanced dual coil 2,4-dinitrophenylhydrazine (DNPH) derivatization method (dual coil/DNPH) allowed the quantitative determination of formaldehyde (HCHO) in ambient air. In this method, traceable HCHO was collected using a coil sampler connected in series and lacking a long sampling tube. It was then analyzed using liquid chromatography followed by UV detection of the DNPH derivatives. The method is based on the reaction of formaldehyde with DNPH to produce 2,4-dinitrophenylhydrazone. The detection limits (3σ) were 0.10–0.40 ppbv with a precision ranging from 0.84 to 4.09% RSD. The results of dual coil/DNPH and conventional DNPH cartridge methods were generally well correlated: HCHO (dual coil/DNPH) = 0.97 (±0.13) vs. HCHO (DNPH Cartridge) + 0.33 (±0.33), r = 0.82. The dual coil/DNPH method was used to measure gaseous HCHO in the atmosphere of Metropolitan Seoul during the summer 2000 and 2001, and in Gwangju during the fall of 2001 and 2002. The daytime mean concentration of HCHO was 4.52 (±5.69) and 3.21 (±1.27) ppbv in Metropolitan Seoul for 10–12 August 2000 and 29–31 May 2001, respectively, and 1.73 (±0.98), 3.04 (±2.25), 2.70 (±1.70), and 2.01 (±2.28) ppbv in Gwangju City during 22–27 September 2001, 17–24 October 2001, 9–13 October 2002, and 28 October to 2 November 2002, respectively. The HCHO in Seoul from 10–12 August 2000 was mainly the result of photochemical processes, while direct emissions from vehicles and long-range transport of air from China contributed during 29–31 May 2001. During 22–27 September 2001, 17–24 October 2001, and 9–13 October 2002 in Gwangju, the HCHO came primarily from photochemical processes, although some air affected by biomass burning admixed in the late afternoon. The increase in the HCHO concentration on 20 October 2001 and from 28 October to 2 November 2002 was attributed mainly to direct emissions from biomass burning in farmland near the measurement site.     

Passive sampling of herbicides combined with effect analysis in algae using a novel high-throughput phytotoxicity assay (Maxi-Imaging-PAM)

We propose to combine a passive sampler for polar organic compounds (POS) with a specific bioassay for phytotoxicity to assess the hazard of herbicidal compounds in surface waters. The POS consisted of an Empore disk coated with styrenedivinylbenzene deployed in a Teflon housing, which has relatively high sampling rates (e.g., approximately 1 L d(-1) for diuron). POS were deployed for 5 days in a small-scale field study in South East Queensland, Australia, in a relatively pristine environment and an urban environment to explore sensitivity towards herbicides and potential influences of non-herbicidal pollutants. Besides chemical analysis of 8 herbicides, a novel bioassay (Maxi-Imaging-PAM, IPAM) was employed to assess the phytotoxic effects of water samples and POS extracts. The IPAM allows rapid assessment of photosynthetic quantum yields of a large number of samples via chlorophyll-fluorescence imaging and the saturation pulse method. Sampling rates for several herbicides from laboratory calibrations were found to be applicable under field conditions. Toxic equivalent concentrations (with reference to the herbicide diuron) were computed from the concentrations determined by chemical analysis and the relative potency (also termed toxic equivalence factor) of the detected herbicides. There was good agreement between diuron equivalent concentrations from chemical analysis and diuron equivalent concentrations determined with the IPAM.     

The problem of using fixed-area subsampling methods to estimate macroinvertebrate richness: a case study with Neotropical stream data

Subsampling has been widely applied in the laboratory to process freshwater macroinvertebrate samples. Currently, many governmental agencies and research groups apply the fixed-count approach, targeting a number of individuals per sample, and at the same time keeping track of the number of quadrats (fraction of the sample) processed. However, fixed-area methods are still in use. The objective of this paper was to evaluate the reliability of macroinvertebrate taxonomic richness estimates developed from processing a standard number of subsampling quadrats (i.e., fixed-area approaches). We used a dataset from 18 tropical stream sites experiencing three different levels of human disturbance (most-, intermediate-, and least-disturbed). With 12 quadrats processed (half the sample), the collection curves started to stabilize, and for more than half of the sites studied, it was possible to sample at least 80 % of the total taxonomic richness of the sample. However, we observed that the minimum number of quadrats to achieve 80 % of taxonomic richness was strongly negatively correlated with the number of individuals collected in each site: the fewer the individuals in a sample, the greater the processed proportion of that sample needed to represent it properly. Thus our results indicate that for any given areal subsampling effort (any fixed fraction of the sample), samples with different numbers of individuals will be represented differently in terms of the proportion of the total number of taxa of the whole samples, those with greater numbers being overestimated and those with fewer numbers being underestimated. Therefore, we do not recommend the use of fixed-area subsampling methods alone if the main purpose is to measure and analyze taxonomic richness; instead, we encourage researchers to use fixed-count approaches for this purpose.