A new sampler for stratified lagoon chemical and microbiological assessments

A sampler was needed for a spatial and temporal study of microbial and chemical stratification in a large swine manure lagoon that was known to contain zoonotic bacteria. Conventional samplers were limited to collections of surface water samples near the bank or required a manned boat. A new sampler was developed to allow simultaneous collection of multiple samples at different depths, up to 2.3 m, without a manned boat. The sampler was tethered for stability, used remote control (RC) for sample collection, and accommodated rapid replacement of sterile tubing modules and sample containers. The sampler comprised a PVC pontoon with acrylic deck and watertight enclosures, for a 12 VDC gearmotor, to operate the collection module, and vacuum system, to draw samples into reusable autoclavable tubing and 250-mL bottles. Although designed primarily for water samples, the sampler was easily modified to collect sludge. The sampler held a stable position during deployment, created minimal disturbance in the water column, and was readily cleaned and sanitized for transport. The sampler was field tested initially in a shallow fresh water lake and subsequently in a swine manure treatment lagoon. Analyses of water samples from the lagoon tests showed that chemical and bacterial levels, pH, and EC did not differ between 0.04, 0.47, and 1.0 m depths, but some chemical and bacterial levels differed between winter and spring collections. These results demonstrated the utility of the sampler and suggested that future manure lagoon studies employ fewer or different depths and more sampling dates.     

Investigation and assessment of volatile organic compounds in water sources in China

456 water samples collected from 152 water sources in 2006 were analyzed for 21 volatile organic compounds (VOCs). Concentrations of 21 VOCs ranged from below method detection limits of the laboratory to 7.65 ??g/L (toluene), but seldom exceeded the concentration limits set in the National Drinking Water Quality Standards (GB5749-2006) or the National Environmental Quality Standards for Surface Water (GB3838-2002) of China. Of the 21 individual VOCs analyzed, 11 VOCs were detected in at least one sample at or above 1.0 ??g/L; 6.6% of the water samples had a detection of at least one VOC at or above 1.0 ??g/L, and 2.6% had a detection of at least two VOCs at or above 1.0 ??g/L. Based on the statistical data of detection frequencies above the method detection limits, 75% of the samples detected at least one VOC, and 65% of the samples detected at least two VOCs. Chloroform, toluene, and 1,2-dichloroethene were the three most frequently detected VOCs, with detection frequencies of 76.97%, 68.42%, and 44.08%, respectively. Volatile halogenated hydrocarbons and gasoline components were the two most frequently detected VOC groups.     

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.     

Application of a Dialysis Sampler to Monitor Phytoremediation Processes

A cylindrical dialysis sampler (1.2 m in length; 5 cm in diameter) was designed and constructed to sample small–scale phytoremediation processes in the root zone of poplar trees. The study site was a 183–tree plantation of hybrid poplars located at Aberdeen Proving Ground, Maryland, at the J–Field Area of Concern. The grove was planted in 1996 to intercept a chlorinated solvent plume containing 1,1,2,2–tetrachloroethane (1,1,2,2–TeCA, trichloroethene (TCE) and daughter products. Two dialysis samplers were installed: one directly in the poplar grove (approximately 0.3 m from the trunk of a mature tree) and the other outside of the grove but in the plume. Data collected included concentrations of chlorinated VOCs, organic acids, chloroacetic acids, Cl⁻, and dissolved gases (ethane, ethene, CH₄, CO₂). At the control location, the VOC profile was dominated by cis– 1,2–dichloroethene (cis–1,2–DCE) and trans–1,2–dichloroethene (trans–1,2–DCE) with concentrations ranging from 0.88-4.5 to 4.4-17.6 mg/L, respectively. Concentrations of VOCs were similar across the vertical profile. At the tree location, 1,1,2,2–TeCA and TCE were the dominant VOCs detected but as opposed to the control location were highly variable within the root zone, with the greatest variability associated with locations in the sampler where roots were observed. This highly variable profile at the tree location is indicative of VOC rhizosphere biodegradation and uptake near the active roots. This variability appears to be on the centimeter scale, emphasizing the importance of these high–resolution samplers for the study of rhizosphere influences.     

Measurement and Interpretation of Concentrations of Urban Atmospheric Organic Compounds

The presence of volatile organic compounds (VOCs) from traffic and other sources in urban areas is a cause for concern about public health. Canister, chemical derivatisation, particulate sampling and adsorption sampling techniques were used to measure VOC concentrations of a wide range of compounds (C6-C40) during a four day campaign in south London with subsequent laboratory analysis of the samples. Compounds quantified included alkanes, mono- and poly-nuclear aromatic hydrocarbons. Also the first sequential measurements of carbonyl compounds (C1-C8) in a UK urban area are presented. Results from canister and adsorption sampling methods are compared. A comparison of the results with other urban data is presented and the temporal variations in VOC concentrations were interpreted with reference to the prevalent wind speeds and directions. The CALINE4 line source dispersion model was generally successful in reproducing the daytime 12 hour average concentrations of selected VOCs.     

Influence of processing parameters on VOC emission from particleboards

Volatile organic compound (VOC) emissions from furnishings have created a major indoor air pollution problem in China. The aim of this study was to investigate the VOC emission of larch particleboard under different processing conditions. VOCs collection chamber, parts per billion VOC monitor, and gas chromatography–mass spectrometer were used to analyze the VOC components and quantities. The results were shown as follows: (1) concentration and emission rate of VOCs were significantly affected by hot-pressing temperature and time. With the increase of hot-pressing temperature and time, both the earlier emission concentration and the amount of total volatile organic compounds increased. (2) The composition of VOCs was also influenced by temperature and time, especially the variety of terpene, benzene, and derivative. The existence and quantities of esters were still the main components of VOCs emissions.     

Spatial Analysis of Volatile Organic Compounds from a Community-Based Air Toxics Monitoring Network in Deer Park,Texas, USA

In the summer of 2003, ambient air concentrations of volatile organic compounds (VOCs) were measured at 12 sites within a 3-km radius in Deer Park, Texas near Houston. The purpose of the study was to assess local spatial influence of traffic and other urban sources and was part of a larger investigation of VOC spatial and temporal heterogeneity influences in selected areas of Houston. Seventy 2-h samples were collected using passive organic vapor monitors. Most measurements of 13 VOC species were greater than the method detection limits. Samplers were located at 10 residential sites, a regulatory air monitoring station, and a site located at the centroid of the census tract in which the regulatory station was located. For residential sites, sampler placement locations (e. g., covered porch vs. house eaves) had no effect on concentration with the exception of methyl tertiary-butyl ether (MTBE). Relatively high correlations (Pearson r > 0.8) were found between toluene, ethylbenzene, and o,m,p-xylenes suggesting petroleum-related influence. Chloroform was not correlated with these species or benzene (Pearson r < 0.35) suggesting a different source influence, possibly from process-related activities. As shown in other spatial studies, wind direction relative to source location had an effect on VOC concentrations.     

Soil Gas Volatile Organic Compound Concentration Contours for Locating Vadose Zone Nonaqueous Phase Liquid Contamination

Diffusion of VOC from cylindrical vadose zone domains contaminatedwith distributed nonaqueous phase liquid is examined in the steadystate approximation. The effects of first-order biodegradation and ofan extended underlying pool of LNAPL floating on the water table belowthe cylindrical domain are explored by means of an orthogonal functionsapproach. The distribution of VOC in the vadose zone above a floatingcircular LNAPL pool of finite size is explored by a numerical method.The results provide information useful in estimating the spacing anddepth at which soil gas samples should be taken in order to detect thepresence of such source areas. Comparison of model results with soilgas VOC measurements at various depths also provides insight into theextent to which natural biodegradation of the VOCs is taking place.     

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.     

Soil sampling and analysis for volatile organic compounds

Concerns over data quality have raised many questions related to sampling soils for volatile organic compounds (VOCs). This paper was prepared in response to some of these questions and concerns expressed by Remedial Project Managers (RPMs) and On-Scene Coordinators (OSCs). The following questions are frequently asked:

1. Is there a specific device suggested for sampling soils for VOCs?
2. Are there significant losses of VOCs when transferring a soil sample from a sampling device (e.g., split spoon) into the sample container?
3. What is the best method for getting the sample from the split spoon (or other device) into the sample container?
4. Are there smaller devices such as subcore samplers available for collecting aliquots from the larger core and efficiently transferring the sample into the sample container?
5. Are certain containers better than others for shipping and storing soil samples for VOC analysis?
6. Are there any reliable preservation procedures for reducing VOC losses from soil samples and for extending holding times?

Guidance is provided for selecting the most effective sampling device for collecting samples from soil matrices. The techniques for sample collection, sample handling, containerizing, shipment, and storage described in this paper reduce VOC losses and generally provide more representative samples for volatile organic analyses (VOA) than techniques in current use. For a discussion on the proper use of sampling equipment the reader should refer to other sources (Acker, 1974; U.S. EPA, 1983; U.S. EPA, 1986a). Soil, as referred to in this report, encompasses the mass (surface and subsurface) of unconsolidated mantle of weathered rock and loose material lying above solid rock. Further, a distinction must be made as to what fraction of the unconsolidated material is soil and what fraction is not. The soil component here is defined as all mineral and naturally occurring organic material that is 2 mm or less in size. This is the size normally used to differentiate between soils (consisting of sands, silts, and clays) and gravels. Although numerous sampling situations may be encountered, this paper focuses on three broad categories of sites that might be sampled for VOCs:

1. Open test pit or trench.
2. Surface soils (<5 ft in depth).
3. Subsurface soils (>5 ft in depth).

     

Continuous, intermittent and passive sampling of airborne VOCs

Long sampling periods are often advantageous or required for measuring air quality and characterizing exposures. However, sampling periods exceeding 8 to 24 h using thermally desorbable adsorbent tube (TDT) samplers for the measurement of airborne volatile organic compounds (VOCs) face several challenges, including maintaining stable and low flow rates, and avoiding breakthrough of the adsorbent. These problems may be avoided using intermittent sampling; however, the literature contains few if any reports that have evaluated this technique in environmental, occupational or other applications. The purpose of this study is to evaluate continuous, intermittent and passive sampling methods using both laboratory and real-world tests. Laboratory tests compared continuous and intermittent (active) samplers in a controlled dynamic test gas generation system. Field tests used side-by-side active and passive samplers in an office, home workshop and four smokers' homes. All samples were analyzed for a wide range of VOCs by GC-MS. In most instances, intermittent sampling yielded better reproducibility (duplicate precision of 10 +/- 6%) than continuous low-flow sampling (18 +/- 5%), in part due to difficulty maintaining low flows. Concentrations obtained using intermittent sampling agreed with those for continuous sampling, with downward biases resulting primarily from errors in flow rate measurements. In the field, more VOC species were detected using active rather than passive sampling. Passive measurements were 12% lower than continuous measurements, a difference attributed to declining uptake rates at higher concentrations over the 3 to 4 d sampling period. Overall, most measurements obtained using the three sampling methods agreed within 20% for a wide range of concentrations (0.1 to 230 microg m(-3)). Both passive and intermittent sampling approaches are suitable for long sampling periods, but intermittent sampling provides greater flexibility with respect to sampling period, and permits the use of multi-bed adsorbents that can capture a wider range of VOCs.     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

Analysis of volatile organic compounds released during food decaying processes

A number of volatile organic compounds (VOCs) including acetone, methyl ethyl ketone, toluene, ethylbenzene, m,p-xylene, styrene, and o- xylene released during food decaying processes were measured from three types of decaying food samples (Kimchi (KC), fresh fish (FF), and salted fish (SF)). To begin with, all the food samples were contained in a 100-mL throwaway syringe. These samples were then analyzed sequentially for up to a 14-day period. The patterns of VOC release contrasted sharply between two types of fish (FF and SF) and KC samples. A comparison of data in terms of total VOC showed that the mean values for the two fish types were in the similar magnitude with 280 ± 579 (FF) and 504 ± 1,089 ppmC (SF), while that for KC was much lower with 16.4 ± 7.6 ppmC. There were strong variations in VOC emission patterns during the food decaying processes between fishes and KC that are characterized most sensitively by such component as styrene. The overall results of this study indicate that concentration levels of the VOCs differed significantly between the food types and with the extent of decaying levels through time.     

Diffusive Sampling of Volatile Organic Compounds in Ambient Air

The Building Research Establishment (BRE) has been using diffusive samplers for the study of VOCs in indoor and outdoor air since 1989. The Perkin Elmer type sampler packed with Tenax TA adsorbent is used for the diffusive sampling of C6-C16 organic compounds. This method was applied in a major study of relationships between the environment and child health carried out during 1990-1993 in the Avon area of the UK. The present paper reports results of an investigation into the repeatability of the sampler in outdoor air and measurements of 6 aromatic hydrocarbons inside and outside a home over a 5 year period and inside and outside an office building over a 12 month period. Both the home and the office were located in Hertfordshire, England. Concentrations of VOCs recorded are similar to those found in the Avon area. Higher concentrations of each of the six compounds were recorded inside the home than outside, whilst greater amounts of benzene and toluene were found inside the office than outside. Seasonal variations in concentrations are observed and measurements recorded outdoors are similar to those recorded by other workers.     

Comparative assessments of VOC emission rates and associated health risks from wastewater treatment processes

With the growing concern regarding emission of volatile organic compounds (VOCs) from wastewater treatment plants (WWTPs), the relationship between the VOC emission rates and the associated public health risks has been rarely discussed. The objective of this study was to examine and compare the VOC emission rates and cancer and non-cancer risks by inhalation intake, using a municipal WWTP in China as an example, with respect to the effects of treatment technologies, VOC species, and seasonal variation. Given the treatment technology considered, the emission rates of VOCs in this study were estimated by means of mass balance or calculated on the molecular level. From the viewpoints of both emission rates and cancer and non-cancer risks, sedimentation was the treatment technology with the highest health risks to the workers. Slightly lower VOC emission rates and health risks than those for sedimentation were observed in anaerobic treatment. Although the aeration significantly enhanced the VOC emission rates in the aerobic treatment process, the associated health risks were limited due to the low VOC concentrations in the gas phase, which were likely attributed to the strong mixing and dilution with fresh air by aeration. Amongst the VOCs investigated, benzene was the VOC with both a relatively high emission rate and health risk, while trichloroethylene possessed a high emission rate but the lowest health risk. Without strong interfacial aeration and turbulence between the water and atmosphere, the effects of treatment technology and seasonal variation on the health risks might be connected to the VOC emission rates, while the effect of VOC species depended considerably on the respective cancer slope factors and reference concentrations; the employment of aeration provided a different conclusion in which the emission rates were enhanced without a significant increase in the related cancer risks. These findings can provide insight into future health risk management and reduction strategies for workers in WWTPs.     

Differences between weekend and weekday ozone levels over rural and urban sites in Southern Italy

Air quality data from a network of 11 monitoring stations in the Apulia region of southern Italy during the summer of 2005 reveal a high frequency of ozone law limit violations. Since ozone is a secondary pollutant, air quality control strategies aimed at reducing ozone concentration are not immediate. Herein, we analyse weekly changes in concentration levels of ozone (O(3)), nitrogen oxides (NO(x)), carbon monoxide (CO), and volatile organic compounds (VOCs), and evaluate how the differences in primary emissions cause changes in the production of ozone. The comparison between weekend and weekday levels of O(3) and its precursors are direct evidence for the existence of the "ozone weekend effect." This effect was observed at all stations with a considerable variation in the overall ozone magnitude, including both traffic stations and non-traffic stations. Data from VOC measurements at traffic stations primarily indicated elevated levels of benzene, toluene, and xylenes (BTX); all of these substances showed an overall decrease over the weekend. A single station indicated levels of non-methane hydrocarbon (NMHC) and PM10, both of which did not demonstrate any weekly cycle. Analysis of weekly and diurnal cycles of O(3), NO(x), CO, NMHC, and PM10 indicates that higher weekend ozone levels result from a reduction in the emission of nitrogen oxides on weekends in VOC-sensitive regimes. This indicates that a reduction in VOC and NO(x) levels would be more effective than NO(x) reduction alone. Our results underscore the need for improved and more efficient VOC measurements.     

Evaluation of VOC measurments in the EXPOLIS study. Air Pollution Exposure Distributions within Adult Urban Urban Populations in Europe

Personal exposures and microenvironment concentrations of 30 target VOCs were measured for 401 participants living in five European cities as a part of the EXPOLIS (Air Pollution Exposure Distributions within Adult Urban Populations in Europe) study. Measurements in Basel used an active charcoal (Carbotech) adsorbent as opposed to the Tenax TA used in the other study centres. In addition, within each centre, personal and microenvironment VOC sampling required different sampling pumps and, because of different sampling durations, different sampling flow rates. Thus, careful testing of the sampling and analysis procedures was required to ensure accuracy and comparability of collected data. Monitor comparison tests using Tenax TA showed a mean VOC concentration ratio of 0.95 between the personal and microenvironment monitors. The LODs for the target VOCs using Tenax TA ranged from 0.7 to 5.2 microg m(-3). The LODs for the 14 target compounds quantifiable using Carbotech ranged from 0.9 to 3.2 microg m(-3). Tenax TA field blanks showed no remarkable contamination with the target VOCs, except benzaldehyde, a known artefact with this adsorbent. Thus, the diffusion barrier system used prevented contamination of Tenax TA samples by passive diffusion during non-sampling periods. Duplicate and parallel evaluations of the Tenax TA and Carbotech showed an average difference of < 17% in VOC concentrations within the sampling methods, but a systematic difference between the methods (Tenax TA: Carbotech concentration ratio = 1.18-2.36). These field evaluations and quality assurance tests showed that interpretation and comparison of the results in any VOC monitoring exercise should be done on a compound by compound basis. It is also apparent that carefully planned and realised QA and QC (QA/QC) procedures are needed in multi-centre studies, where a common sampling method and laboratory analysis technique are not used, to strengthen and simplify the interpretation of observed VOC levels between participating centres.     

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.     

A comparison of sampling and analysis methods for low-ppbC levels of volatile organic compounds in ambient air

A carefully designed study was conducted during the summer of 1998 to collect samples of ambient air by canisters and compare the analysis results to direct sorbent preconcentration results taken at the time of sample collection. Thirty-two 1 h sample sets were taken, each composed of a "near-real-time" sample analyzed by an autoGC-MS XonTech 930/Varian Saturn 2000 system, and Summa and Silco canisters. Hourly total non-methane organic carbon (TNMOC), ozone, and meteorological measurements were also made. Each canister was analyzed on the autoGC-MS system for a target list of 108 volatile organic compounds (VOCs) and on a manual cryosampling GC-FID system. Comparisons were made between the collection and analysis methods. Because of the low sample loading (150-250 ppbC TNMOC), these comparisons were a stringent test of sample collection and analysis capabilities. The following specific conclusions may be drawn from this study. Reasonable precision (within 15% mean difference of duplicate analyses from the same canister) can be obtained for analyses of target VOCs at low-ppbC concentrations. Relative accuracy between the GC-MS and GC-FID analysis methods is excellent, as demonstrated by comparisons of analyses of the same canisters, if measurements are sufficiently above the detection limits. This is especially significant as the GC-MS and GC-FID were independently calibrated. While statistically significant differences may be observed between the results from canister and near-real-time samples, the differences were generally small and there were clear correlations between the canister results and the near-real-time results. Canister cleanliness limits detection below the EPA Method TO-14 acceptance standard of 0.2 ppbv (0.2-2 ppbC for target analytes).