A simplified method for sampling and analysis of high volume surface water for organic contaminants using XAD-2

A simple compressed-gas driven system for field processing and extracting water for subsequent analyses of hydrophobic organic compounds is presented. The pumping device is a pneumatically driven pump and filtration system that can easily clarify at 4 L/min. The extraction device uses compressed gas to drive filtered water through two parallel XAD-2 resin columns, at about 200 mL/min. No batteries or inverters are required for water collection or processing. Solvent extractions were performed directly in the XAD-2 glass columns. Final extracts are cleaned-up on Florisil cartridges without fractionation and contaminants analyzed by GC-MS. Method detection limits (MDLs) and recoveries for dissolved organic contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides are reported along with results of surface water analysis for the San Francisco Bay, CA.     

The use of Whatman 41 filter papers for high volume aerosol sampling

The efficiency of Whatman 41 filter paper as an air sampling medium is discussed. Literature and our own data indicate that this media is unsuitable for low-volume sampling, but is suitable for high-volume sampling.     

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700 °C and 400 °C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5 cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700 °C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400 °C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700 °C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe.Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.     

Field validation of an active sampling cartridge as a passive sampler for long-term carbonyl monitoring

A carbonyl sampler originally designed for the active sampling method (Sep-Pak XPoSure) was used for long-term passive sampling, and its applicability as a passive sampler was examined through field experiments. The uptake rates of passive sampling were determined experimentally from collocated passive and active samplings for various sampling periods. The obtained uptake rates of formaldehyde, acetaldehyde, and acetone were 1.48, 1.23, and 1.08 mL/min, respectively. These uptake rates were consistent for a wide range of the sampling term (12 hr-2 weeks). Uptake rates of each carbonyl were proportional to the diffusion coefficients of each. Therefore, the ratios of diffusion coefficients were used to calculate the uptake rates of carbonyls for which the rates were not determined experimentally. Lower limits of determination were 2.16-17.5 microg/m3 for 2-week sampling. It was confirmed that 2-week monitoring of carbonyl concentrations up to 118-229 microg/m3 was possible. Relative standard deviations of the passive method generated from the repeatability test were 2-12.3% error for five samplings, and the recovery efficiencies were larger than 90%. Thus, the passive sampler was found to be highly suitable for long-term monitoring of carbonyl compounds.     

Measuring emissions of organophosphate flame retardants using a passive flux sampler

Flame retardants are used in polymers to reduce the flammability of building materials, electric appliances, fabric and papers. In recent years, organophosphate flame retardants have been used as substitutes for polybrominated flame retardants (BFRs). In Japan, the amount of organophosphate flame retardants used in 2001 was about five times more than in 2000. Recently, several studies have shown the health concerns for some organophosphate flame retardants. Little research has been performed on the emission of organophosphate flame retardants, especially the relationship between content and emissions. In this study, a new type of passive sampler was developed to measure emissions of organophosphate flame retardants from plastic materials. With this sampler, emissions from polyvinyl chloride wallpaper samples with different content of tris(2-chloroisopropyl)phosphate (TCPP) at different temperatures were examined. The observed maximum emissions of TCPP from 1, 3, 5, 10 and 20 w/w% content wallpaper materials were 262.3, 452.6, 644.8, 1119.1 and 2166.8 μg m⁻² h⁻¹, respectively. Emissions from 5% TCPP content materials at 40 and 60 °C were 1135.7 and 2841.2 μg m⁻² h⁻¹, respectively. A significantly positive correlation between the flux of TCPP and the TCPP content of the wallpaper samples was observed. A linear relationship was found between the inverse of temperature and the logarithm of TCPP emission. The results imply that the use of materials with a high organophosphate flame retardant content can lead to high emission rates in high-temperature indoor environments.     

The utility of distributed air volume sets when sampling ambient air using solid adsorbents

Use of solid adsorbents for air sampling always raises questions of adequate retention, blank corrections and artifact formation. Universally valid answers to these questions are unavailable. Collection of a small set of data by sampling over a large range of air volume can provide situation-specific indications of data quality not possible with the more usual tandem bed approach. Further, it does so in a direct simple way that is especially useful in monitoring applications. The distributed air volume sampling approach is illustrated using Tenax as the adsorbent.     

Dilution-based emissions sampling from stationary sources: Part 1--Compact sampler methodology and performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.     

Comparison of the particle size distribution of heavy-duty diesel exhaust using a dilution tailpipe sampler and an in-plume sampler during on-road operation

Originally constructed to develop gaseous emission factors for heavy-duty diesel trucks, the U.S. Environmental Protection Agency's (EPA) On-Road Diesel Emissions Characterization Facility has been modified to incorporate particle measurement instrumentation. An electrical low-pressure impactor designed to continuously measure and record size distribution data was used to monitor the particle size distribution of heavy-duty diesel truck exhaust. For this study, which involved a high-mileage (900,000 mi) truck running at full load, samples were collected by two different methods. One sample was obtained directly from the exhaust stack using an adaptation of the University of Minnesota's air-ejector-based mini-dilution sampler. The second sample was pulled from the plume just above the enclosed trailer, at a point approximately 11 m from the exhaust discharge. Typical dilution ratios of about 300:1 were obtained for both the dilution and plume sampling systems. Hundreds of particle size distributions were obtained at each sampling location. These were compared both selectively and cumulatively to evaluate the performance of the dilution system in simulating real-world exhaust plumes. The data show that, in its current residence-time configuration, the dilution system imposes a statistically significant bias toward smaller particles, with substantially more nanoparticles being collected than from the plume sample.     

Identification of a reactive degradation zone at a landfill leachate plume fringe using high resolution sampling and incubation techniques

Vertical small-scale variation in phenoxy acid herbicide degradation across a landfill leachate plume fringe was studied using laboratory degradation experiments. Sediment cores (subdivided into 5 cm segments) were collected in the aquifer and the sediment and porewater were used for microcosm experiments (50 experiments) and for determination of solid organic carbon, solid-water partitioning coefficients, specific phenoxy acid degraders and porewater chemistry. Results from a multi-level sampler installed next to the cores provided information on the plume position and oxygen concentration in the groundwater. Oxygen concentration was controlled individually in each microcosm to mimic the conditions at their corresponding depths. A highly increased degradation potential existed at the narrow plume fringe (37.7 to 38.6 masl), governed by the presence of phenoxy acids and oxygen. This resulted in the proliferation of a microbial population of specific phenoxy acid degraders, which further enhanced the degradation potential for phenoxy acids at the fringe. The results illustrate the importance of fringe degradation processes in contaminant plumes. Furthermore, they highlight the relevance of using high-resolution sampling techniques as well as controlled microcosm experiments in the assessment of the natural attenuation capacity of contaminant plumes in groundwater.     

Evaluation of high volume particle sampling and sample handling protocols for ambient urban air mutagenicity determinations.

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM10 Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22 degrees C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at -70 degrees C to -80 degrees C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set.(ABSTRACT TRUNCATED AT 250 WORDS)     

Comparison of a novel passive sampler to standard water-column sampling for organic contaminants associated with wastewater effluents entering a New Jersey stream

Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.     

PCB mass transfer coefficients determined by application of a water surface sampler

A water surface sampler (WSS) was employed in combination with greased surface deposition plates (GSDPs) to measure the particulate dry deposition and gas exchange of polychlorinated biphenyls (PCBs) in Chicago, IL. Vapor phase PCB fluxes were calculated by subtracting the particulate fluxes obtained from GSDPs from total (particulate+gas) fluxes obtained from the WSS. Vapor phase PCB fluxes were divided by ambient air concentrations measured with a high volume sampler to calculate overall gas phase PCB mass transfer coefficients (K(G)). The calculated average PCB MTC was 0.54+/-0.47 cm s(-1). This experimentally determined average gas phase overall mass transfer coefficient, K(G), agreed well with the ones reported from studies using similar techniques and agreed well with modeled values obtained using MTC correlations developed for the WSS.     

A study on emission of phthalate esters from plastic materials using a passive flux sampler

Phthalate esters are used as plasticizer in many plastics, and several studies have shown their toxicity. Phthalate esters are gradually emitted over time, and so it is conceivable that they pose a significant health risk. This study aims to investigate the temperature dependence of the emissions of various phthalate esters and to estimate the health risks of these emissions at various temperatures. A passive-type sampler was developed to measure the flux of phthalate esters from the surface of plastic materials. With this sampler, we examined three widely used plastic materials: synthetic leather, wallpaper and vinyl flooring. The observed maximum emissions of diethyl phthalate, dibutyl phthalate, and diethylhexyl phthalate (DEHP) from these materials at 20°C were 0.89, 0.77, and 14 μg m⁻² h⁻¹, respectively. Emissions at 80°C were 2.8, 4.5×10², and 1.5×10³ μg m⁻² h⁻¹, respectively. The results showed this temperature dependence is determined primarily by the type of phthalate ester and less so by the type of material. The estimation from the results of temperature dependence indicated the concentration of DEHP in a vehicle left out in the sunshine during the day can exceed the recommended levels of Japan Ministry of Health, Labour and Welfare.     

Lead isotopes in rainfall collected by a sequential sampler in suburban Tokyo

Sequential rainfall collections were obtained with a 1-mm precipitation interval at a suburban site in Tokyo. The lead–isotope composition of each fraction was precisely determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The results showed that lead isotopes clearly changed during a single rainfall event for all rainfall events investigated, and large variations were observed for three specific events. In these three events, the values of the lead isotopes in the initial stage of rainfall (wash-out stage) were similar to the so-called common lead. As precipitation proceeded, the lead isotopes tended to be more radiogenic, and in the later stage (rain-out stage) they were highly radiogenic (up to ^{206, 207, 208}Pb/²⁰⁴Pb=29.26, 26.03, and 63.64, respectively). The source of lead in the rain-out stage completely differed from that in the wash-out stage for these events. A simple mixing model with two end members (rain-out lead and wash-out lead) could explain the isotopic variations. Preliminary trajectory analysis indicated that the highly radiogenic lead was emitted and transported from South-West China. Coal combustion could be a candidate for rain-out stage lead by a selective emission of radiogenic isotopes (²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb). A selective emission mechanism is discussed. The origin of the wash-out lead may have been local and derived from a mixture of urban particulates, e.g., particles from automobile exhaust, city incinerators, roadside dust, and factory exhaust.     

Sizing of atmospheric particulates with a high volume cascade impactor

This article describes the development of a high volume cascade impactor with a sampling rate of 20 ft³/min that can be powered by high volume blowers in common use for air sampling. With this impactor it is now possible to collect enough sample of atmospheric particulates in a 24 hour period to conveniently determine an aerodynamic size distribution of suspended particulates by gravimetric analysis. The impactor has four stages and an after-filter and separates particles from the air stream by inertial impaction. The effective cutoff diameters for the stages are 7.0, 3.3, 2.0, and 1.1 microns. The after-filter traps the submicron material.