Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.     

Modelling the Distribution and Quality of Sand and Gravel Resources in 3D: a Case Study in the Thames Basin,UK

Three-dimensional (3D) models are often utilised to assess the presence of sand and gravel deposits. Expanding these models to provide a better indication of the suitability of the deposit as aggregate for use in construction would be advantageous. This, however, leads to statistical challenges. To be effective, models must be able to reflect the interdependencies between different criteria (e.g. depth to deposit, thickness of deposit, ratio of mineral to waste, proportion of ‘fines’) as well as the inherent uncertainty introduced because models are derived from a limited set of boreholes in a study region. Using legacy borehole data collected during a systematic survey of sand and gravel deposits in the UK, we have developed a 3D model for a 2400 km² region close to Reading, southern England. In developing the model, we have reassessed the borehole grading data to reflect modern extraction criteria and explored the most suitable statistical modelling technique. The additive log-ratio transform and the linear model of coregionalization have been applied, techniques that have been previously used to map soil texture classes in two dimensions, to assess the quality of sand and gravel deposits in the area. The application of these statistical techniques leads to a model which can be used to generate thousands of plausible realisations of the deposit which fully reflect the extent of model uncertainty. The approach offers potential to improve regional-scale mineral planning by providing an enhanced understanding of sand and gravel deposits and the extent to which they meet current extraction criteria.

     

Determination of aluminium in groundwater samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium complexes

The paper presents the results of aluminium determinations in ground water samples of the Miocene aquifer from the area of the city of Poznań (Poland). The determined aluminium content amounted from <0.0001 to 752.7 μg L(-1). The aluminium determinations were performed using three analytical techniques: graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of aluminium determinations in groundwater samples for particular analytical techniques were compared. The results were used to identify the ascent of ground water from the Mesozoic aquifer to the Miocene aquifer in the area of the fault graben. Using the Mineql+ program, the modelling of the occurrence of aluminium and the following aluminium complexes: hydroxy, with fluorides and sulphates was performed. The paper presents the results of aluminium determinations in ground water using different analytical techniques as well as the chemical modelling in the Mineql+ program, which was performed for the first time and which enabled the identification of aluminium complexes in the investigated samples. The study confirms the occurrence of aluminium hydroxy complexes and aluminium fluoride complexes in the analysed groundwater samples. Despite the dominance of sulphates and organic matter in the sample, major participation of the complexes with these ligands was not stated based on the modelling.     

Polycyclic aromatic hydrocarbon (PAH) concentration and composition determined in farmed blue mussels (Mytilus edulis) in a sea loch pre- and post-closure of an aluminium smelter

Concentrations of polycyclic aromatic hydrocarbons (2- to 6-ring parent and branched PAH) from an actively producing commercial shellfish farm in Loch Leven, Scotland, were found in excess of 4000 ng g(-1) wet weight tissue. These concentrations were considerably greater than had been recorded from mussels sampled elsewhere around the Scottish mainland. The PAH composition of the mussels from Loch Leven was dominated by the 5-ring, parent compounds; benzo[b]fluoranthene was the dominant compound. This data was consistent with the source being a discharge from an aluminium smelter. The individual compounds benz[a]anthracene, benzo[a]pyrene and dibenz[a,h]anthracene returned values of 304 ng g(-1), 446 ng g(-1) and 39 ng g(-1) respectively; these were well above the 15 ng g(-1) pragmatic guideline limit. Over the two year monitoring period, the concentrations of these compounds in mussels from Loch Etive, a reference location, ranged between 'not detected' and 4 ng g(-1)(for benz[a]anthracene). Mussels were transferred from a clean location to Loch Leven which demonstrated that the rate of uptake of PAH was rapid. Following closure of the aluminium smelter, the PAH concentrations in mussels decreased. Differences between the two sites within Loch Leven were noted with the longer-term impact remaining greater for the mussels closer to the original point discharge.     

Evaluation of an Exposure Assay to Measure Uptake of Sediment Pah by Fish

The ecological risks of polynuclear aromatic hydrocarbons (PAH) in aquatic sediments will vary with both toxicity and bioavailability to aquatic biota. While there are standardized protocols to test the acute toxicity of sediment-borne compounds to aquatic invertebrates, there are none for assessing bioavailability to fish. We found that sediment-borne PAH caused an exposure-dependent induction of cytochrome P450 (CYP1A) enzymes in rainbow trout (Oncorhynchus mykiss) fingerlings exposed in semi-static 96 h bioassays, as shown by increased activity of ethoxyresorufin-o-deethylase (EROD). Assuming that PAH are taken up by trout due to partitioning from organic and inorganic constituents of sediments, we tested the effect of different test variables on bioaccumulation using induction as an index of exposure. EROD activity increased with exposure of fish to increasing volumes of sediments containing PAH, i.e., with increasing ratios of sediment to water. Uptake of single compounds from sandy sediments did not differ from uptake from clay or low organic (7% LOI — loss on ignition) sediments, but decreased when organic content was very high (58% LOI). Maximum induction was observed within 24~h of exposure and at 7.5^C relative to 15, 22, or 28^C. Storage and handling techniques had minor effects on sediment EROD induction potency. Absolute EROD activity was greater in white sucker (Catostomus commersoni) a benthic species, than in trout, a pelagic species. However, when basal (negative control) activity was accounted for, there was no difference in response between the species. Together, these experiments provide a basis for developing a standard protocol to test the bioavailability to fish of sediment-borne PAH.     

Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

An assessment of the bioavailability of persistent organic pollutants from contaminated soil

A procedure to assess the bioavailability of persistent organic pollutants (POPs) from soil samples has been developed. The procedure is based on the use of simulated in vitro gastrointestinal extraction to remove POPs from soil matrices. The level of recovery, using this approach, is assessed following liquid-liquid extraction (LLE) and analysis by gas chromatography-mass selective detection (GC-MSD). The remaining soil residue is then extracted using pressurised fluid extraction (PFE) followed by GC-MSD analysis to assess the residual fraction. The residual fraction is monitored to determine the unavailable fraction i.e. not available for absorption in the gastrointestinal tract of humans. The procedure was applied to four soil samples i.e. an aged, spiked soil and three certified reference materials (CRMs) contaminated with POPs. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II), phenols (cresol, TCP and PCP), and base neutral compounds (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from aged, spiked soil following extraction with gastric fluid ranged from 0.8 to 8.3% while following intestinal extraction ranged from 5.5 to 13.5%, irrespective of POP. Recoveries of pesticides (lindane, endosulfan I, endrin, DDE, DDD and endosulfan II) from CRM 805-050 following extraction with gastric fluid were below the limit of detection while following intestinal extraction ranged from 5.3 to 12.8%. Recoveries of phenols (cresol, TCP and PCP) from CRM 401-225 following extraction with gastric fluid ranged from 1.6 to 2.0% while following intestinal extraction ranged from 4.1 to 5.4%. Recoveries of base neutral acid analytes (hexachloroethane, acenaphthene, dibenzofuran, fluorene and hexachlorobenzene) from CRM 107-100 following extraction with gastric fluid ranged from 1.4 to 4.0% while following intestinal extraction ranged from 6.6 to 12.7%. It has been found that the majority of POPs present i.e. >75%, would be excreted if consumed and not be absorbed in the gastrointestinal tract of humans.     

Towards the establishment of an environmental quality standard for aluminium in surface waters

Steps taken to establish an environmental quality standard (EQS) for aluminium are described. The range of water types in England and Wales and the concentrations of low molecular weight (active) forms of aluminium have been assessed in order to evaluate the risk posed by aluminium in surface waters. Levels of low molecular weight forms of aluminium are mainly in the range 0-25 microg l(-1). Data suggest that dissolved aluminium might form the basis of a reasonably useful prediction of active aluminium leading to a simplified approach to compliance monitoring of an EQS set in terms of active aluminium.     

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils may be useful for further remediation to reduce the bioavailability of Pb in contaminated soils.     

The depositional setting of the Late Quaternary sedimentary fill in southern Bannu basin,Northwest Himalayan fold and thrust belt,Pakistan

Geostatistical variogram and inversion techniques combined with modern visualization tools have made it possible to re-model one-dimensional electrical resistivity data into two-dimensional (2D) models of the near subsurface. The resultant models are capable of extending the original interpretation of the data to depict alluvium layers as individual lithological units within the 2D space. By tuning the variogram parameters used in this approach, it is then possible to visualize individual lithofacies and geomorphological features for these lithologic units. The study re-examines an electrical resistivity dataset collected as part of a groundwater study in an area of the Bannu basin in Pakistan. Additional lithological logs from boreholes throughout the area have been combined with the existing resistivity data for calibration. Tectonic activity during the Himalayan orogeny uplifted and generated significant faulting in the rocks resulting in the formation of a depression which subsequently has been filled with clay-silt and dirty sand facies typical of lacustrine and flood plain environments. Streams arising from adjacent mountains have reworked these facies which have been eroded and replaced by gravel-sand facies along channels. It is concluded that the sediments have been deposited as prograding fan shaped bodies, flood plain, and lacustrine deposits. Clay-silt facies mark the locations of paleo depressions or lake environments, which have changed position over time due to local tectonic activity and sedimentation. The Lakki plain alluvial system has thus formed as a result of local tectonic activity with fluvial erosion and deposition characterized by coarse sediments with high electrical resistivities near the mountain ranges and fine sediments with medium to low electrical resistivities towards the basin center.     

Assessment of phenanthrene bioavailability in aged and unaged soils by mild extraction

It has become apparent that the threat of an organic pollutant in soil is directly related to its bioavailable fraction and that the use of total contaminant concentrations as a measure of potential contaminant exposure to plants or soil organisms is inappropriate. In light of this, non-exhaustive extraction techniques are being investigated to assess their appropriateness in determining bioavailability. To find a suitable and rapid extraction method to predict phenanthrene bioavailability, multiple extraction techniques (i.e., mild hydroxypropyl-β-cyclodextrin (HPCD) and organic solvents extraction) were investigated in soil spiked to a range of phenanthrene levels (i.e., 1.12, 8.52, 73, 136, and 335 μg g^− 1 dry soil). The bioaccumulation of phenanthrene in earthworm (Eisenia fetida) was used as the reference system for bioavailability. Correlation results for phenanthrene suggested that mild HPCD extraction was a better method to predict bioavailability of phenanthrene in soil compared with organic solvents extraction. Aged (i.e., 150 days) and fresh (i.e., 0 day) soil samples were used to evaluate the extraction efficiency and the effect of soil contact time on the availability of phenanthrene. The percentage of phenanthrene accumulated by earthworms and percent recoveries by mild extractants changed significantly with aging time. Thus, aging significantly reduced the earthworm uptake and chemical extractability of phenanthrene. In general, among organic extractants, methanol showed recoveries comparable to those of mild HPCD for both aged and unaged soil matrices. Hence, this extractant can be suitable after HPCD to evaluate risk of contaminated soils.     

Predicting bioavailability and bioaccumulation of arsenic by freshwater clam Corbicula fluminea using valve daily activity

There are many bioindicators. However, it remains largely unknown which metal–bioindicator systems will give the reasonable detection ranges of bioavailable metals in the aquatic ecosystem. Various experimental data make the demonstration of biomonitoring processes challenging. Ingested inorganic arsenic is strongly associated with a wide spectrum of adverse health outcomes. Freshwater clam Corbicula fluminea, one of the most commonly used freshwater biomomitoring organisms, presents daily activity in valve movement and demonstrates biotic uptake potential to accumulate arsenic. Here, a systematical way was provided to dynamically link valve daily activity in C. fluminea and arsenic bioavailability and toxicokinetics to predict affinity at arsenic-binding site in gills and arsenic body burden. Using computational ecotoxicology methods, a valve daily rhythm model can be tuned mathematically to the responsive ranges of valve daily activity system in response to varied bioavailable arsenic concentration. The patterned response then can be used to predict the site-specific bioavailable arsenic concentration at the specific measuring time window. This approach can yield predictive data of results from toxicity studies of specific bioindicators that can assist in prediction of risk for aquatic animals and humans.     

Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations

Gas chromatography-isotope ratio mass spectrometry (GC-IRMS) has made it possible to analyze natural stable isotope ratios (e.g., (13)C/(12)C, (15)N/(14)N, (2)H/(1)H) of individual organic contaminants in environmental samples. They may be used as fingerprints to infer contamination sources, and may demonstrate, and even quantify, the occurrence of natural contaminant transformation by the enrichment of heavy isotopes that arises from degradation-induced isotope fractionation. This review highlights an additional powerful feature of stable isotope fractionation: the study of environmental transformation mechanisms. Isotope effects reflect the energy difference of isotopologues (i.e., molecules carrying a light versus a heavy isotope in a particular molecular position) when moving from reactant to transition state. Measuring isotope fractionation, therefore, essentially allows a glimpse at transition states! It is shown how such position-specific isotope effects are "diluted out" in the compound average measured by GC-IRMS, and how a careful evaluation in mechanistic scenarios and by dual isotope plots can recover the underlying mechanistic information. The mathematical framework for multistep isotope fractionation in environmental transformations is reviewed. Case studies demonstrate how isotope fractionation changes in the presence of mass transfer, enzymatic commitment to catalysis, multiple chemical reaction steps or limited bioavailability, and how this gives information about the individual process steps. Finally, it is discussed how isotope ratios of individual products evolve in sequential or parallel transformations, and what mechanistic insight they contain. A concluding session gives an outlook on current developments, future research directions and the potential for bridging the gap between laboratory and real world systems.     

Determination and evaluation of hexavalent chromium in power plant coal combustion by-products and cost-effective environmental remediation solutions using acid mine drainage

The chromium species leaching from a coal combustion fly ash landfill has been characterized as well as a novel approach to treat leachates rich in hexavalent chromium, Cr(VI), by using another natural waste by-product, acid mine drainage (AMD), has been investigated during this study. It is observed that as much as 8% (approximately 10 microg g(-1) in fly ash) of total chromium is converted to the Cr(VI) species during oxidative combustion of coal and remains in the resulting ash as a stable species, however, it is significantly mobile in water based leaching. Approximately 1.23 +/- 0.01 microg g(-1) of Cr(VI) was found in the landfill leachate from permanent deposits of aged fly ash. This study also confirmed the use of AMD, which often is in close proximity to coal combustion by-product landfills, is an extremely effective and economical remediation option for the elimination of hexavalent chromium in fly ash generated leachate. Speciated isotope dilution mass spectrometry (SIDMS), as described in EPA Method 6800, was used to analytically evaluate and validate the field application of the ferrous iron and chromate chemistry in the remediation of Cr(VI) runoff.     

Statistical needs in national water quality monitoring programs

The concept that a few well chosen, strategically placed, water quality stations can provide valuable scientific information to water managers is common to many countries. Historically within Canada, water quality regional networks (Great Lakes network, Prairie Provinces Water Board network, Long Range Transport of Airborne Pollutants network, etc.) have been successfully operating for many years. This paper will describe the difficulties associated with developing a national water quality network for a country the size of Canada. In particular, it will describe some of the statistical tools presently being used in regional networks which are suitable for a national network, and discuss the need to develop new statistical tools for environmental monitoring in the 1990's.     

The potential of remote sensing for monitoring land cover changes and effects on physical geography in the area of Kayisdagi Mountain and its surroundings (Istanbul)

The effect of land cover change, from natural to anthropogenic, on physical geography conditions has been studied in Kayisdagi Mountain. Land degradation is the most important environmental issue involved in this study. Most forms of land degradation are natural processes accelerated by human activity. Land degradation is a human induced or natural process that negatively affects the ability of land to function effectively within an ecosystem. Environmental degradation from human pressure and land use has become a major problem in the study area because of high population growth, urbanization rate, and the associated rapid depletion of natural resources. When studying the cost of land degradation, it is not possible to ignore the role of urbanization. In particular, a major cause of deforestation is conversion to urban land. The paper reviews the principles of current remote sensing techniques considered particularly suitable for monitoring Kayisdagi Mountain and its surrounding land cover changes and their effects on physical geography conditions. In addition, this paper addresses the problem of how spatially explicit information about degradation processes in the study area rangelands can be derived from different time series of satellite data. The monitoring approach comprises the time period between 1990 and 2005. Satellite remote sensing techniques have proven to be cost effective in widespread land cover changes. Physical geography and particularly natural geomorphologic processes like erosion, mass movement, physical weathering, and chemical weathering features etc. have faced significant unnatural variation.     

Speciation of heavy metals in biosolids of wastewater treatment plants at Mysore,Karnataka, India

Urban wastewater treatment leads to the generation of large quantities of biosolids. Accumulation of biosolids is a problem of environmental relevance due to the existence of heavy metals in the biosolids. Determination of total metal in biosolid provides information relating pollution levels. Determination of their mobilization capacity and behaviour in the environment is an important task. An experimental approach commonly used for studying the mobility, transport and bioavailability of metal in biosolids is the use of selective sequential extraction procedure. In the present study an attempt has been made to study the heavy metal properties in biosolid samples collected from urban wastewater treatment plants located at Mysore, Karnataka. Few heavy metals selected for the present study are cadmium, chromium, copper, iron, nickel and zinc. The concentration of these metals in biosolids and their partition in different fractions are studied. The speciation of metals based on the sequential extraction scheme was carried out. The concentration of heavy metals is lower than that established by European legislation. The residual fraction has the maximum percentage of heavy metals whereas, only a small fraction of heavy metals (Fe, Zn and Cd) are extracted in the most soluble fractions, exchangeable and carbonate fractions.     

Tracing sources of coal combustion using stable sulfur isotope ratios in epilithic mosses and coals from China

In China, coal combustion is the most important source of atmospheric sulfur pollution. Moss sulfur isotopic signatures have been believed to hold source-specific information that can serve as a fingerprint to identify atmospheric sulfur sources. In cities where only local coals were combusted, we observed a good correspondence of average sulfur isotope ratios in urban mosses (Haplocladium microphyllum) to the values of local coals (δ(coals) = 1.455δ(mosses)- 3.945, R(2) = 0.975, p = 0.01). But if different types of coals were combusted, we did not know whether moss sulfur isotope ratios can indicate mixed coals. To confirm this, using a mixing model we estimated the ratios of imported coal to local coals at cities where both coals were used. We found that the estimated ratios at large cities (>1 million people) where both coals were used were similar to the reported ratios in their respective provinces. For small cities (<0.5 million people) in Jiangxi Province and other provinces, the estimated ratios were higher than the reported ratios because the relatively cheaper local coals were less used in all the small cities except in cities where local coal deposits were found nearby. The comparison results showed that moss sulfur isotope is a useful tool for indicating coal-derived sulfur even in cities where mixed coals were combusted.     

Spatial contaminant heterogeneity: quantification with scale of measurement at contrasting sites

Material within the terrestrial environment is rarely homogeneously distributed, either spatially or temporally. One consequence of heterogeneity is that uncertainty is usually generated in measurements that are taken with the aim of characterising the environment. For example, a measurement of analyte concentration within soil taken from one sampling location on contaminated land can vary substantially when compared against another sample taken at effectively the same nominal location. The measurement uncertainty arising from the heterogeneity can substantially limit the reliability of the interpretations made upon environmental investigations. The sampling uncertainty usually outweighs the analytical uncertainty from the laboratory, often by a factor of 20 or more. One approach to reducing the uncertainty is to design a more suitable sampling strategy. This might be achieved by predicting the degree of heterogeneity prior to the investigation, but this is often difficult to achieve accurately. Another approach, which was investigated here, is to actually characterise the heterogeneity prior to the main investigation using rapid and inexpensive technology, such as in situ measurement techniques. In situ portable X-ray fluorescence (PXRF) and X-ray microprobe (XMP) techniques were employed to test the feasibility of this approach. Two contrasting contaminated land sites were chosen to characterise the two-dimensional spatial heterogeneity of heavy metal contamination in topsoil at a range of scales (50 m to 0.001 m). The spatial heterogeneity of contaminants, expressed as relative standard deviations, was found to differ between the two sites by a factor of two, largely due to the mode of deposition of pollution. The study also indicated that the heterogeneity did not change systematically with the scale of measurement between sampling locations at either site.     

Assessment of the bioavailability of cadmium in Jamaican soils

Extraordinary geogenic concentrations of cadmium (Cd) have been reported for some Jamaican soils. However, the bioavailability of the metal in these soils remains unknown. Here, the bioavailability of Cd in selected Jamaican soils was investigated through the determination of total and sequentially extractable concentrations in paired soil–plant (yam; Dioscorea sp.) samples (n?=?24), using neutron activation analysis and atomic absorption spectroscopy as primary analytical techniques. Our results indicate that total soil Cd varied widely (2.2–148.7 mg kg^?1), and on average, total extractable Cd accounted for ~55 % of the total soil Cd. The exchangeable and oxidizable species averaged 1.5 and 6.4 % of the total Cd, respectively, and, based on Spearman analysis, are the best predictors of yam Cd. There is also good evidence to suggest that variation in the bioavailability of the metal is in part controlled by the geochemical characteristics of the soils analyzed and is best explained by pH, cation exchange capacity (CEC) and organic matter content (% LOI).