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).

     

Woodstove emission measurement methods: Comparison and emission factors update

On February 26, 1988, the U.S. Environmental Protection Agency promulgated Standards of Performance for residential wood heaters, or woodstoves. Over the past several years, a number of field studies have been undertaken to determine the actual level of emission reduction achieved by new technology woodstoves in everyday use. These studies have required the development and use of particulate and gaseous emission sampling equipment compatible with operation in private houses. Since woodstoves are tested for certification in the laboratory using EPA Methods 5G and 5H, it is of substantial interest to determine the correlation between these regulatory methods and the in-house equipment. Two in-house sampling systems have been used most widely. One is an intermittent, pump-driven particulate sampler which collects particulate and condensable organics on a filter and organic adsorbent resin. Oxygen concentration is measured by a sensor in the sample line. The sampler is controlled by a data logger which also records other parameters of interest. The second system uses an evacuated cylinder as the motive force. Particulate and condensable organics are collected in a condenser and dual filter. The sampler operates continuously whenever the stack temperature is above the set point. Average stack gas concentrations are measured from the evacuated cylinder at the conclusion of the sampling period. Both samplers were designed to operate unattended for 1-week periods. A large number of tests have been run comparing Methods 5G and 5H to both of the field samplers. This paper presents these comparison data and determines the relationships between laboratory certification sampling methods and field samplers.     

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

The efficacy of protoporphyrin as a predictive biomarker for lead exposure in canvasback ducks: Effect of sample storage time

We used 363 blood samples collected from wild canvasback dueks (Aythya valisineria) at Catahoula Lake, Louisiana, U.S.A. to evaluate the effect of sample storage time on the efficacy of erythrocytic protoporphyrin as an indicator of lead exposure. The protoporphyrin concentration of each sample was determined by hematofluorometry within 5 min of blood collection and after refrigeration at 4 °C for 24 and 48 h. All samples were analyzed for lead by atomic absorption spectrophotometry. Based on a blood lead concentration of 0.2 ppm wet weight as positive evidence for lead exposure, the protoporphyrin technique resulted in overall error rates of 29%, 20%, and 19% and false negative error rates of 47%, 29% and 25% when hematofluorometric determinations were made on blood at 5 min, 24 h, and 48 h, respectively. False positive error rates were less than 10% for all three measurement times. The accuracy of the 24-h erythrocytic protoporphyrin classification of blood samples as positive or negative for lead exposure was significantly greater than the 5-min classification, but no improvement in accuracy was gained when samples were tested at 48 h. The false negative errors were probably due, at least in part, to the lag time between lead exposure and the increase of blood protoporphyrin concentrations. False negatives resulted in an underestimation of the true number of canvasbacks exposed to lead, indicating that hematofluorometry provides a conservative estimate of lead exposure.The U.S. Government's right to retain a non-exclusive, royalty-free licence in and to any copyright is acknowledgedDeceased     

Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

A simple,cost-effective multispecies toxicity test using organisms with a cosmopolitan distribution

Difficulties in making accurate, ecosystem-level predictions of environmental effects of chemicals, mixtures, and effluents based solely on the results of tests on single species have necessitated the development of more environmentally realistic, predictive testing methods. This paper describes a multispecies, community-level toxicity test based on the colonization of artificial substrates by microbial species. Tests examined the colonization of initially barren polyurethane foam artificial substrates by Protozoa from a species source colonized in a natural system. Differences in colonization were examined in microecosystems amended with low levels of cadmium, a very toxic heavy metal, and TFM, an organic biocide used against larval sea lamprey. Tests examined differences in colonization over 28 days. For cadmium, effect levels were estimated to be near 1 g 1^–1, in the low range of effect levels determined from chronic single species tests. For TFM, effect levels were estimated to be between 1 and 10 ppm, overlapping the concentrations used in environmental applications. The colonization response, which depends on naked microbial cells reproducing and migrating through toxicant amended water to new substrates, is very sensitive. Tests based on colonization can be adapted to use species from a target receiving system or can use species from a designated natural source. Field validation of these tests can employ nearly identical methods to those used in laboratory studies to assess the accuracy of predictions based on test system data.     

The analysis of monitoring data with the aid of time-series analysis

Methods derived from time-series analysis are proposed for processing monitoring data. The necessity for the use of these methods is demonstrated. In a case study time-series analysis was applied to assess the impact of the closure of the Grevelingen estuary (S. W. Netherlands) in 1971 on a local wintering population of Oystercatchers (Haematopus ostralegus) in the adjacent Oosterschelde estuary.Communication No. 328 of the Delta Institute for Hydrobiological Research.     

Distribution of suspended particulate matter with trace element composition and apportionment of possible sources in the Raniganj coalfield,India

Ambient air monitoring for suspended particulate matter was carried over a period of one year in some coal mining areas of the Raniganj coalfield. Concentrations of seven elements in suspended particulate matter were determined. The set of data obtained was analysed to determine the sources of trace elements by factor analysis. The data could be interpreted on the basis of five factors. These factors are attributed to various sources of particulate matter by noting the dependence of factors on the elements.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.     

Effect of Humic Acid on the Bioavailability of γ-Hexachlorocyclohexane in Marsilea Minuta (L.)

Effect of various concentrations of humic acid (0.2 to 1%) on thebioavailability of -HCH in vegetative clones of theaquatic fern Marsilea minuta was studied in a staticexperimental bioassay system on different photoperiods. Additionof humic acid showed the reduction in the bioavailability of-HCH in all the photoperiods (72 hr light to 144 hrlight) at the interval of 16 hr light (L) and 8 hr dark (D) inboth aerial and submerged portion as compared to controlindicating its protective role in toxicity.