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).

     

Analysing the sensitivity behaviour of two hydrology models

Recently, the New Morris Method has been presented as an effective sensitivity analysis tool for mathematical models. The New Morris Method estimates the sensitivity of an output parameter to a given set of input parameters (first-order effects) and the extent these parameters interact with each other (second-order effects). This method requires the specification of two parameters (runs and resolution) that control the sampling of the output parameter to determine its sensitivity to various inputs. The criteria for these parameters have been set on the analysis of a well-behaved analytical function (see Cropp and Braddock, Reliab. Eng. Syst. Saf. 78:77–83, 2002), which may not be applicable to other physical models that describe complex processes. This paper will investigate the appropriateness of the criteria from (Cropp and Braddock, 2002) and hence the effectiveness of the New Morris Method to determine the sensitivity behaviour of two hydrologic models: the Soil Erosion and Deposition System and Griffith University Representation of Urban Hydrology. In the first case, this paper will separately analyse the sensitivity of an output parameter on a set of input parameters (first- and second-order effects) for each model and discuss the physical meaning of these sensitivities. This will be followed by an investigation into the sampling criteria by exploring the convergence of the sensitivity behaviour for each model as the sampling of the parameter space is increased. By comparing these trends to the convergence behaviour from Cropp and Braddock (2002), we will determine how well the New Morris Method estimates the sensitivity for each model and whether the sampling criteria are appropriate for these models. It will be shown that the New Morris Method can provide additional insight into the functioning of these models, and that, under a different metric, the sensitivity behaviour of these models does converge confirming the sampling criteria set by Cropp and Braddock.     

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     

Cadmium and zinc source assessment in the Sepetiba Bay and basin region

Industrial and weathering inputs of Cd and Zn to the Sepetiba Bay and basin were assessed, based on production parameters obtained from local environment and industry authorities, and literature data. The results are compared with similar evaluations from other coastal regions and field data obtained in measuring Zn and Cd transport by rivers, direct run-off and atmospheric deposition in the region. Cadmium and zinc inputs to the bay increased by three orders of magnitude relative to pre-industrial fluxes and presently reach up to 1.6 and 180 tonnes per year for Cd and Zn, respectively, which represents a large input-to-area ratio, and explains the high concentration of these metals previously reported in the estuarine biota and sediments of Sepetiba Bay. Industrial activities, mainly metallurgical and chemical, comprise 94% and 84% of the total Cd and Zn inputs to the Bay. This figure identifies the point sources as being responsible for the environmental contamination and for regional poisoning risks.     

Scenario Analysis for the San Pedro River, Analyzing Hydrological Consequences of a Future Environment

Studies of future management and policy options based on different assumptions provide a mechanism to examine possible outcomes and especially their likely benefits and consequences. The San Pedro River in Arizona and Sonora, Mexico is an area that has undergone rapid changes in land use and cover, and subsequently is facing keen environmental crises related to water resources. It is the location of a number of studies that have dealt with change analysis, watershed condition, and most recently, alternative futures analysis. The previous work has dealt primarily with resources of habitat, visual quality, and groundwater related to urban development patterns and preferences. In the present study, previously defined future scenarios, in the form of land-use/land-cover grids, were examined relative to their impact on surface-water conditions (e.g., surface runoff and sediment yield). These hydrological outputs were estimated for the baseline year of 2000 and predicted twenty years in the future as a demonstration of how new geographic information system-based hydrologic modeling tools can be used to evaluate the spatial impacts of urban growth patterns on surface-water hydrology.     

Working backwards to move forwards: Graph-based connectivity metrics for reserve network selection

In this paper we apply graph theory in a reserve selection exercise to explore the tradeoffs between maintaining connectivity and minimizing the total area of a protected area network. Rather than focus on a single organism, we used a multi-species approach and looked at the tradeoff curves for organisms with varying dispersal abilities. We first generated the tradeoff curves using a graph-based metric to determine the importance of individual patches for maintaining connectivity. We then performed an analogous set of analyses using patch size as a surrogate measure of importance.     

Microbiological characteristics in a zero-valent iron reactive barrier

Zero-valent iron (Fe⁰)-based permeable reactive barriertreatment has been generating great interest for passivegroundwater remediation, yet few studies have paid particularattention to the microbial activity and characteristics withinand in the vicinity of the Fe⁰-barrier matrix. The presentstudy was undertaken to evaluate the microbial population andcommunity composition in the reducing zone of influence byFe⁰ corrosion in the barrier at the Oak Ridge Y-12 Plantsite. Both phospholipid fatty acids and DNA analyses were usedto determine the total microbial population and microbialfunctional groups, including sulfate-reducing bacteria,denitrifying bacteria, and methanogens, in groundwater andsoil/iron core samples. A diverse microbial community wasidentified in the strongly reducing Fe⁰ environment despitea relatively high pH condition within the Fe⁰ barrier (up topH 10). In comparison with those found in the backgroundsoil/groundwater samples, the enhanced microbial populationranged from 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. Inaddition, microbial community composition appeared to change overtime, and the bacterial types of microorganismsincreased consistently as the barrier aged. DNA analysisindicated the presence of sulfate-reducing and denitrifyingbacteria in the barrier and its surrounding soil. However, theactivity of methanogens was found to be relatively low,presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidenceof a diverse microbial population within and in the vicinity ofthe iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevityand enduring efficiency of the Fe⁰ barriers are yet to be evaluated.     

Attributes of reliable long-term landscape-scale studies: Malpractice insurance for landscape ecologists

Monitoring long-term change in forested landscapes is an intimidating challenge with considerable practical, methodological, and theoretical limitations. Current field approaches used to assess vegetation change at the plot-to-stand scales and nationwide forest monitoring programs may not be appropriate at landscape scales. We emphasize that few vegetation monitoring programs (and, thus, study design models) are designed to detect spatial and temporal trends at landscape scales. Based primarily on advice from many sources, and trial and error, we identify 14 attributes of a reliable long-term landscape monitoring program: malpractice insurance for landscape ecologists. The attributes are to: secure long-term funding and commitment; develop flexible goals; refine objectives; pay adequate attention to information management; take an experimental approach to sampling design; obtain peer-review and statistical review of research proposals and publications; avoid bias in selection of long-term plot locations; insure adequate spatial replication; insure adequate temporal replication; synthesize retrospective, experimental, and related studies; blend theoretical and empirical models with the means to validate both; obtain periodic research program evaluation; integrate and synthesize with larger and smaller scale research, inventory, and monitoring programs; and develop an extensive outreach program. Using these 14 attributes as a guide, we describe one approach to assess the potential effect of global change on the vegetation of the Front Range of the Colorado Rockies. This self-evaluation helps identify strengthes and weaknesses in our program, and may serve the same role for other landscape ecologists in other programs.     

From proposal to decision: Suggestions for tightening up the “NEPA process”

Although the process of documenting compliance with NEPA (the National Environmental Policy Act) requires no drastic revisions, it can be managed more rigorously. Suggestions for revision can be grouped under five major steps: 1) getting a complete proposal from the applicant; 2) getting the decision-making process onto the right decision-making path; 3) modifying the applicant's proposal 4) going down a shorter path through the EA/FONSI (environmental assessment and finding of no significant impact) or through categorical exclusion review; and 5) going down the longer path through the EIS. Step 2 is perhaps the most critical, because there a decision must be made whether to write an EA/FONSI or an EIS, on the basis of whether the proposal would “significantly affect … the … environment.” In the past, this decision has not always been made promptly or rigorously. Accordingly, we suggest that the agency responsible for NEPA compliance should develop a system (a “black box”), consisting of a core group of specialists working with an interdisciplinary team, using sophisticated techniques for modeling impacts and directing both their research and their writing according to the concept of significance. By determining more efficiently and reliably whether the impacts of a proposal would be significant, such an approach would improve management of the total process.