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.     

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.     

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.     

Multivariate analysis of the bioaccumulation of polychlorinated biphenyls (PCBs) in the marine pelagic food web from the southern part of the Baltic Sea,Poland

The concentration, pattern, bioaccumulation and biomagnification features of many chlorobiphenyl congeners including non- and mono-ortho chlorine substituted members have been determined in a pelagic food chain including mixed phyto- and zooplankton, herring (Clupea harengus), harbour porpoise (Phocoena phocoena) and black cormorants (Phalacrocorax carbo sinensis) collected from the southern part of the Baltic Proper. TCDD (tetrachlorodibenzo-p-dioxin) toxic equivalents (TEQs) in plankton, herring, harbour porpoise and cormorants were 0.42, 5.3, 79 and 2,700 pg g(-1) lipid weight, respectively. Concentrations of total polychlorinated biphenyls (PCBs) in plankton, herring, harbour porpoise and cormorants were 1.9, 120, 8700 and 2,100 ng g(-1) wet weight (210, 1,300, 10,000 and 42,000 ng g(-1) lipid weight) respectively. Herring, harbour porpoise and black cormorant apparently bioaccumulate many PCBs found in their food, and the values of the bioaccumulation factors (BAFs) for PCBs were approximately 10 in herring, 35 in harbour porpoise and up to 300 in breast muscle of cormorants. Harbour porpoise clearly is able to metabolize the most toxic non-ortho PCBs (no. 77, 126 and 169) and a few mono-ortho PCBs (no. 114, 123 and 156), while all non- and mono-ortho PCBs are bioaccumulated by herring. Penta-, hexa- and hepta-CBs were the dominatant homologue classes both in the muscle tissue and liver. PCB congeners nos. 201, 209, 172/192, 194 and 195 were characterized by the largest BAFs (between 100 and 300). Principal component analysis has been used to analyse the interdependences and differences in the CB congener accumulation patterns between the components of the investigated pelagic food web.     

A national framework for monitoring and reporting on environmental sustainability in Canada

In 1991, a collaborative project to revise the terrestrial component of a national ecological framework was undertaken with a wide range of stakeholders. This spatial framework consists of multiple, nested levels of ecological generalization with linkages to existing federal and provincial scientific databases. The broadest level of generalization is the ecozone. Macroclimate, major vegetation types and subcontinental scale physiographic formations constitute the definitive components of these major ecosystems. Ecozones are subdivided into approximately 200 ecoregions which are based on properties like regional physiography, surficial geology, climate, vegetation, soil, water and fauna. The ecozone and ecoregion levels of the framework have been depicted on a national map coverage at 1:7 500 000 scale. Ecoregions have been subdivided into ecodistricts based primarily on landform, parent material, topography, soils, waterbodies and vegetation at a scale (1:2 000 000) useful for environmental resource management, monitoring and modelling activities. Nested within the ecodistricts are the polygons that make up the Soil Landscapes of Canada series of 1:1 000 000 scale soil maps. The framework is supported by an ARC-INFO GIS at Agriculture Canada. The data model allows linkage to associated databases on climate, land use and socio-economic attributes.     

Development of Ecological Land Classification and mapping in support of forest management in northern Newfoundland,Canada

For the sustainable development of forest land, as recently prescribed by the Canadian Forest Strategy, a land classification project in northern Newfoundland was initiated to support the local forest management activities. The method adopted here is a modification of the Canadian Committee for Ecological Land Classification's (CCELC) system, and it applies various levels of mapping to uniform areas based on geomorphology, soils, vegetation, climate, water, and fauna.In this study, all CCELC levels were mapped; resulting maps were digitized and imported into a Geographic Informations System (GIS). The GIS data base contained the following maps: 1) digital terrain model, 2) bedrock geology, 3) surficial geology, 4) forest inventory, and 5) various levels of the ecological land classification, including Vegetation Types at the lowest level. In addition to the mapping, mensurational data were analyzed to provide stand and stock tables for each of the forest types, including growth curves that could be entered into specific forest growth modelling systems to predict wood supply scenarios based upon different management interventions.     

Reduction of SO2 emissions by ammonia gas during unstaged combustion

The reduction of SO₂ by the addition of ammonia gas has been studied in a 2 m high fluidized bed combustor having a 30 cm static bed height and a freeboard height of 170 cm. Ammonia gas was injected at 52 cm above the distributor where the temperature is ca. 700° C by an uncooled stainless steel tube injector. Experiments were carried out to investigate the effects of amminia gas injection on sulphur dioxide emissions at unstaged conditions of: (i) excess air level, (ii) NH₃:SO₂ molar ratio, (iii) fluidizing velocity and (iv) bed height.A maximum reduction of 75% in SO₂ emissions was found at 40% excess air, at an NH₃:SO₂ molar ratio of 5.4. The onset of SO₂ reduction occurred at an NH₃:SO₂ ratio of 1.5 However, the most effective ratio was found to be between 3 and 5. Fluidizing velocity and bed height were also found to have significant influence on SO₂ reduction.It is difficult to determine how the SO₂ reduction varied with operating conditions. When ammonia is added in the main combustor zone, the temperature is much higher than that required for the occurrence of sulphur dioxide-ammonia and sulphur trioxide-ammonia reactions. However, this paper points out the significance of ammonia addition in the reduction of sulphur dioxide.     

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.