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).

     

Relevance of radiation compensation litigation to compensation for toxic exposures

Several recent court decisions add to the growing body of law concerning the responsibility of Government in radiation matters and the quantum of proof needed to show causation between radiation exposures and certain types of cancer and leukemia. The courts have also been addressing a wide range of compensation claims for exposures to toxic chemicals with demonstration of causation being a particularly difficult task. Meanwhile, the Congress has been attempting to legislate a far reaching administrative and judicial framework for compensating toxic victims, including an easing of burden-of-proof requirements for demonstrating causation and a broadening of the basis for admissibility of scientific evidence. Drawing parallels between radiation and toxic exposure problems can be both instructive and misleading. Some of the technical issues are quite similar, including the importance of person-specific exposure estimates and of epidemiological studies. However, the uncertainties associated with toxic exposures are usually far greater, and the scientific data base for relating exposures and effects is much more uncertain.     

Dose-time-response functions for toxic chemicals

In many situations, the effect of a toxic chemical on a biological system depends on both the intensity and the duration of exposure. The dependence on the time dimension can be the expression of a range of processes including the physical accumulation of toxic chemicals or their metabolites and the functional accumulation of damage. Measures and functions that have been used to describe this dependence are reviewed.Some of these functions are compared through a case study of the neurotoxicity of methylmercury. Use is made of data that indicates a dependency between the blood concentration at which monkeys were exposed and the length of time before damage was detected. Several exposure functions are fitted to these data and their appropriateness is compared. Using the most appropriate function, an exposure-response relationship is developed using probit analysis. An alternative data analysis procedure is also investigated. The apparent threshold after a 100 day exposure is estimated to be greater by a factor of 3–5 compared to the threshold for chronic exposure. Applying this factor to man, the blood concentration threshold for chronic exposure is estimated to be 40–170 ppb, a finding consistent with recent reports of neurological damage in humans exposed below the generally accepted threshold.     

Problems of correlation of global and local monitoring of air pollution

1. The Air Polluttion Monitoring System has got a significant development of late, which is in direct relation with a considerable extention and improvement of the observation network in cities and industrial areas, with creation of a new network for assessing regional and global background of the atmosphere pollution, as well as with the wide involvement of meteorologists to monitoring organization.
2. While developing a new global monitoring system, it is necessary to take into account its relationship with the local monitoring within the region of air pollution sources, i.e. at the \lsimpact\rs level. The need in such an account is dictated first of all by the physics of pollutant spreading that states: changes in air pollution over large territories must be in a certain agreement with greater changes in the vicinity of emission sources. Methods applied in the global and local monitoring have also a number of common peculiarities. White organizing regional network for observations of the background pollution of the atmosphere twin stations (one of the pair of stations located outside the city boundaries in a small community, and the other, in the nearest city with the population of 200–400 thousand inhabitants) were established in the U.S.S.R. and in a number of socialist countries in Europe.
3. Implementation of the twin-station principles in the U.S.S.R. has contributed to data interpretation and representativity assessment as well as to correction of the station location. Observation results from the Soviet background stations and those abroad have been compared by now according to a number of indices.
4. The correlation of monitoring systems of various scales tells positively both on mutual improvement and completion of observational methods. The methods of obtaining integral characteristics of air pollution were used for the global monitoring, in particular spectral actinometric observations and chemical analysis of the precipitation composition. Now they find still wider employment. Thus methods of spectral actinometric measurements and data processing were used to estimate the degree of aerosol pollution of a number of industrial centres. The theory of solar radiation spreading and aerosol contents determination in urban atmosphere has also been developed. It is a generalization of an earlier developed theory, used to estimate global atmosphere pollution basing on actinometric data. The organization of precipitation collection and analysis on a network of stations around Leningrad and in Donbass area enables us to compare the admixture content in precipitations falling in industrial and agricultural areas.
5. A considerable increase of possibilities to measure microconcentrations of sulphur dioxide, nitrogen oxides and of a number of other pollutants is connected with the use of solid solvents for sampling. Their use will allow to avoid establishment of special laboratories at background stations and only send samples by post for their analysis in centralized laboratories.

They will also allow to considerably increase precision and accuracy of measurements. The international comparisons of methods of air pollution measurements on the background level allow to judge about the effiency of these methods.     

Determination of biomass burning emission factors: Methods and results

Biomass burning, in a broad sense, encompasses different burning practices, including open and confined burnings, and different types of vegetation. Emission factors of gaseous or particulate trace compounds are directly dependent both on the fuel type and the combustion process. Emission factors are generally calculated by stoichiometric considerations using the carbon mass balance method, applied either to combustion chamber experiments or to field experiments based on ground-level measurements or aircraft sampling in smoke plumes. There have been a number of experimental studies in the last 10 years to investigate wildfires in tropical, temperate, or boreal regions. This article presents an overview of measurement methods and experimental data on emission factors of reactive or radiatively active trace compounds, including trace gases and particles. It focuses on fires in tropical regions, that is, forest and savanna fires, agricultural burns, charcoal production, use of fuelwood, and charcoal combustion.     

Characterization of microbial communities from coastal waters using microarrays

Molecular methods, including DNA probes, were used to identify and enumerate pathogenic Vibrio species in the Chesapeake Bay; our data indicated that Vibrio vulnificus exhibits seasonal fluctuations in number. Our work included a characterization of total microbial communities from the Bay; development of microarrays that identify and quantify the diversity of those communities; and observation of temporal changes in those communities. To identify members of the microbial community, we amplified the 16S rDNA gene from community DNA isolated from a biofilm sample collected from the Chesapeake Bay in February, 2000. The resultant 75 sequences were 95% or more similar to 7 species including two recently described Shewanella species, baltica and frigidimarina, that have not been previously isolated from the Chesapeake. When the genera of bacteria from biofilm after culturing are compared to those detected by subcloning amplified 16S fragments from community DNA, the cultured sample exhibited a strong bias. In oysters collected in February, the most common bacteria were previously unknown. Based on our 16S findings, we are developing microarrays to detect these and other microbial species in these estuarine communities. The microarrays will detect each species using four distinct loci, with the multiple loci serving as an internal control. The accuracy of the microarray will be measured using sentinel species such as Aeromonas species, Escherichia coli, and Vibrio vulnificus. Using microarrays, it should be possible to determine the annual fluctuations of bacterial species (culturable and non-culturable, pathogenic and non-pathogenic). The data may be applied to understanding patterns of environmental change; assessing the health of the Bay; and evaluating the risk of human illness associated with exposure to and ingestion of water and shellfish.     

Fractionation of butyltin species during sample extraction and preparation for analysis

Solvent extraction and evaporative concentration steps are often used in procedures for the measurement of butyltins in environmental samples. As part of a larger study utilizing radiolabeled butyltins, the loss and fractionation of butyltins during sample preparation was investigated. TBT, DBT, and MBT were extracted from acidified seawater by hexane with efficiencies of about 95–99, 50–60 and 11% respectively. In addition, losses of about 70% of DBT were found during evaporative concentration of hexane. A variety of sediment extraction procedures were tested and none were found to be highly efficient for total butyltin extraction.     

Life-history parameters and vertical distribution of Maurolicus muelleri in Masfjorden in summer

Population characteristics, individual life-history variables, feeding and vertical distribution of the mesopelagic fish Müller's pearlside Maurolicus muelleri collected in 1990 in Masfjorden, western Norway, are reported as well as environmental variables from the fjord. Minimum size at maturity was far smaller than reported from previous investigations in the same region. Fecundity was size-dependent and total egg numbers were higher than reported from other investigations of M. muelleri world wide, while the number of maturing eggs was far lower than observed in the same region earlier. Food concentration in the fjord was an order of magnitude lower than previous early summer observations, and several factors indicated that feeding opportunities may have been low for a long period. Daily feeding rate (g prey g^-1 fish) decreased with increasing fish size. These observations fit well with a model of maximizing fitness by means of a flexible size at maturity. Minimum age at maturity seems to be achieved at the expense of fecundity. M. muelleri was concentrated in a 20 to 30 m deep sound scattering layer (SSL). The SSL stayed close to the surface during the night and at 100 to 180 m during the daytime. The vertical position of the SSL varied instantaneously with changes in surface light intensity, remaining at 10^-3 to 10^-4 mol m^-1 s^-1 at the top of the SSL. Stomach fullness was highest during the night; feeding intensity seems to have been peaked at dusk. Cladocerans were the main prey ranked by number, copepods by biomass. Intake of large copepods increased with fish size.