Experimental approaches for size-based metal speciation in rivers

A review of the different methodologies employed to fractionate and characterize riverine suspended particulate matter is presented. The importance of size-based metal speciation is underlined and the possibility of studying it by the Sedimentation Field Flow Fractionation (SdFFF) technique is illustrated. The studies on the metal load in river Suspended Particulate Matter (SPM) performed over the last ten years are critically reviewed focusing on the different methods employed to collect, concentrate and size-fractionate samples. The fact that there is no homogeneity in methods and data collection in this field is underlined. Among the different fractionation techniques, Field Flow Fractionation (FFF) methodologies have proved to be a good approach to study the role of SPM in metal load and transport. The possibility of studying size-based metal speciation using the SdFFF technique is presented and the importance of metal speciation in rivers is underlined.     

Persistence of LNAPL sources: relationship between risk reduction and LNAPL recovery

Light nonaqueous phase liquids (LNAPLs), such as fuels, are the source of much soil and groundwater contamination. Though the mobility of LNAPLs is limited in many environments, dissolved-phase components, such as benzene, can produce groundwater plumes that are more mobile than the LNAPL source. In such a setting, it is commonly assumed that recovery of the LNAPL will result in a reduction in risk associated with the dissolved phase. This paper synthesizes several existing multiphase and chemical transport solutions into a single linked methodology that predicts concentrations of soluble constituents within and downgradient of LNAPL source zones from dissolution of those constituents into groundwater flowing through and below LNAPL sources. This approach has been applied to a variety of LNAPL spill conditions. For biodegradable compounds, these analyses show that the period of time where the dissolved-phase plume is expanding is very small compared to the duration of most LNAPL sources, and that the downgradient extent is generally less than about 100 m for BTEX compounds. Therefore, the risk to receptors, as measured by the maximum downgradient extent of dissolved-phase plume or the maximum concentration of these compounds at a downgradient receptor, is generally unrelated to the longevity of the LNAPL sources. The maximum downgradient extent of the dissolved-phase plume is determined almost entirely by the groundwater velocity and the biodegradation rate. These analyses further demonstrate that recovery of LNAPL by hydraulic methods is often ineffective at reducing risk. Except in coarse-grained soils or intermediate soils with significant LNAPL saturations, free-product recovery approaches do not result in significant reductions in the longevity of downgradient dissolved-phase contamination. Further, for biodegradable constituents, remediation does not result in a near-term decrease in the downgradient extent of contamination. Cleanup methods that act to change the composition of the LNAPL source are more effective at reducing the downgradient concentrations, particularly for fine-grained soils or when LNAPL saturations are low.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

Rethinking remediation: mine reclamation,environmental justice,and relations of care

ABSTRACT

To date, research on mine remediation in North America has focused primarily on technical management; relatively less is known about the historical, political and social dimensions of remediation. Remediation, as a continuation of the mining process, alters local landscapes and economies and can be both dangerous and beneficial for surrounding communities. Because remediation projects tend to focus on the technical aspects of clean-up, such projects risk overlooking the environmental injustices associated with past development and obscuring blame or responsibility from industry and government for environmental degradation. Insofar as it is understood as cleaning up or repairing environmental damage, remediation is generally seen as “doing the good” and is less amenable to political or ethical challenges based on community concerns or values. This paper argues that greater attention needs to be paid to public participation and justice concerns associated with cleaning up mine sites. Drawing from the literatures on ecological restoration, environmental justice, reconciliation, discard studies, and matters of care, we highlight critical, yet overlooked issues in the remediation of post-mining landscapes. We argue that remediation projects present a unique opportunity for the negotiation and articulation of morals, values, histories, and physical experiences associated with mine sites and we seek to re-frame remediation as an ongoing, creative process of community healing.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Deposition velocities to Sorbus aria, Acer campestre, Populus deltoides X trichocarpa 'Beaupré', Pinus nigra and X Cupressocyparis leylandii for coarse, fine and ultra-fine particles in the urban environment

Trees are effective in the capture of particles from urban air to the extent that they can significantly improve urban air quality. As a result of their aerodynamic properties conifers, with their smaller leaves and more complex shoot structures, have been shown to capture larger amounts of particle matter than broadleaved trees. This study focuses on the effects of particle size on the deposition velocity of particles (Vg) to five urban tree species (coniferous and broadleaved) measured at two field sites, one urban and polluted and a second more rural. The larger uptake to conifers is confirmed, and for broadleaves and conifers Vg values are shown to be greater for ultra-fine particles (Dp < 1.0 microm) than for fine and coarse particles. This is important since finer particles are more likely to be deposited deep in the alveoli of the human lung causing adverse health effects. The finer particle fraction is also shown to be transported further from the emission source; in this study a busy urban road. In further sets of data the aqueous soluble and insoluble fractions of the ultra-fines were separated, indicating that aqueous insoluble particles made up only a small proportion of the ultra-fines. Much of the ultra-fine fraction is present as aerosol. Chemical analysis of the aqueous soluble fractions of coarse, fine and ultra-fine particles showed the importance of nitrates, chloride and phosphates in all three size categories at the polluted and more rural location.     

Sampling and analyses of colloids at the Drigg low level radioactive waste disposal site

Water samples have been extracted from inside (from standpipes) and from outside (from boreholes) of the trenches at the low level radioactive waste disposal site at Drigg in Cumbria, UK. The samples were taken anaerobically from between 8.5 and 10.0 m below the surface using a submersible pump at low flow rates to ensure that the waters in the standpipes and boreholes were maintained at constant levels. To ensure representative samples, the Eh, pH. conductivity, temperature, iron and dissolved oxygen concentrations of the waters were taken during initial purging and during sampling. The gross tritium, gross non-tritium beta, gross alpha and gamma activities of each sample were determined using suitable sample preparation and counting techniques. Samples were then anaerobically, sequentially filtered through 12 microm, 1 microm, 30 kDa and 500 Da filter membranes. The filtrates were analysed for gross alpha, gross non-tritium beta and gamma activities. SEM and STEM analyses were used to determine the colloid population. An energy dispersive analyser on the SEM was used to determine the major elements present in the colloids. UV-visible spectrophotometry, fluorescence spectrophotometry and high performance size exclusion liquid chromatography were used to analyse the waters before and after treatment with ion exchange materials to determine whether natural organic matter was present in the waters. Results showed that two major types of colloids (iron containing colloids and silicon containing colloids) were present in the waters. There were also a small number of other colloids that contain, as major elements, aluminium, calcium and chromium. Organic colloids were also present. The majority of the radioactivity in the waters was due to tritium. Waters taken from outside the trenches contained low levels of non-tritium beta activities and alpha activities which were lower than the minimum detectable amount. Waters taken from the trenches contained non-tritium beta activities and low levels of alpha emitters. Filtration of the trench waters showed that some of the alpha activity was retained by the 30 kDa and 500 Da membranes suggesting that this activity was associated with small colloids. Radioactivity was not found to be associated with colloids present in the waters taken from outside the trenches. Possible reasons for this observation could be that radionuclide bearing colloids have not yet reached the far-field or that the radionuclide concentration is diluted to below the minimum detectable amount. After concentrating two of the samples by factors of x20 and x 16 respectively, 2.4+/-0.1 and 0.6+/-0.1 Bq dm(-3) of 137Cs were measured.     

Genetic analysis of Pinus banksiana and Pinus resinosa populations from stressed sites contaminated with metals in Northern Ontario (Canada)

The Sudbury region in Canada is known for the mining and smelting of high-sulphide ores containing nickel, copper, iron and precious metals. Although reports provide information of metal levels in soil and plants, knowledge of genetic effects on plants growing in contaminated areas is limited. The main objective of this study was to characterise the level of genetic diversity in Pinus banksiana and Pinus resinosa populations from the Sudbury (Ontario) region using microsatellite markers. Soil samples were analysed for concentrations of metals. High levels of metal contents in soil were observed within short distances of the smelter compared with control sites. The level of genetic diversity was very low for P. resinosa populations and moderate for P. banksiana samples. Observed heterozygosity was fivefold higher in P. banksiana populations than P. resinosa populations studied. Overall, 17 and 24% of the total genetic diversity were attributed to differences among populations for P. banksiana and P. resinosa, respectively. In general, the inbreeding was significantly higher in P. resinosa populations than P. banksiana populations and gene flows were relatively low in both species. No significant trend of the levels of genetic diversity for metal contaminated and uncontaminated sites was found.     

Urban woodlands: their role in reducing the effects of particulate pollution

In recent years a substantial research effort has focused on the links between particulate air pollution and poor health. As a result the PM10 value has been set as a measure of such pollutants which can directly cause illness. Due to their large leaf areas relative to the ground on which they stand and the physical properties of their surfaces, trees can act as biological filters, removing large numbers of airborne particles and hence improving the quality of air in polluted environments. The role of vegetation and urban woodlands in reducing the effects of particulate pollution is reviewed here. The improvement of urban air quality achieved by establishing more trees in towns and cities is also illustrated.