Collateral benefits and hidden hazards of soil arsenic during abatement assessment of residential lead hazards

Abatement of soil-lead hazards may also reduce human exposure to other soil toxins, thereby achieving significant collateral benefits that are not accounted for today. This proposition was tested with the specific case of soil-arsenic, where 1726 residential soil samples were collected and analyzed for lead and arsenic. The study found that these two toxins coexisted in most samples, but their concentrations were weakly correlated, reflecting the differing sources for each toxin. Collateral benefits of 9% would be achieved during abatement of the lead-contaminated soils having elevated arsenic concentrations. However, a hidden hazard of 16% was observed by overlooking elevated arsenic concentrations in soils having lead concentrations not requiring abatement. This study recommends that soil samples collected under HUD programs should be collected from areas of lead and arsenic deposition and tested for arsenic as well as lead, and that soil abatement decisions consider soil-arsenic as well as soil-lead guidelines.     

In situ transformations of fine lead oxide particles in different soils

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.     

Effectiveness of urea in enhancing the extractability of 2,4,6-trinitrotoluene from chemically variant soils

One of the major challenges in developing an effective phytoremediation technology for 2,4,6-trinitrotoluene (TNT) contaminated soils is limited plant uptake resulting from low solubility of TNT. The effectiveness of urea as a solubilizing agent in increasing plant uptake of TNT in hydroponic systems has been documented. Our preliminary greenhouse experiments using urea were also very promising, but further characterization of the performance of urea in highly-complex soil-solution was necessary. The present study investigated the natural retention capacity of four chemically variant soils and optimized the factors influencing the effectiveness of urea in enhancing TNT solubility in the soil solutions. Results show that the extent of TNT sorption and desorption varies with the soil properties, and is mainly dependent on soil organic matter (SOM) content. Hysteretic desorption of TNT in all tested soils suggests irreversible sorption of TNT and indicates the need of using an extractant to increase the release of TNT in soil solutions. Urea significantly (p < 0.0001) enhanced TNT extraction from all soils, by increasing its solubility at the solid/liquid interface. Soil organic matter content and urea application rates showed significant effects, whereas pH did not exert any significant effect on urea catalysis of TNT extraction from soil. The optimum urea application rates (125 or 350 mg kg⁻¹) for maximizing TNT extraction were within the limits set by the agronomic fertilizer-N rates used for major agricultural crops. The data obtained from this batch study will facilitate the optimization of a chemically-catalyzed phytoremediation model for cleaning up TNT-contaminated soils.     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Atmospheric heavy metal deposition accumulated in rural forest soils of southern Scandinavia

Thirty-three years of measurements of atmospheric heavy metal (HM) deposition (bulk precipitation) in Denmark combined with European emission inventories form the basis for calculating a 50-year accumulated atmospheric input to a remote forest plantation on the island of Laesoe. Soil samples taken in two depths, 0-10cm and 10-20cm, at eight forest sites at the island were used to determine the increase in HM content in the eolian deposited top soils of the plantation. Concentrations of lead (Pb), cadmium (Cd), copper (Cu), zinc (Zn), vanadium (V), nickel (Ni) and arsenic (As) were determined in atmospheric deposition and in soils. The accumulated atmospheric deposition is of the same magnitude as the increase of these metals in the top soil.     

Factors affecting EDTA extraction of lead from lead-contaminated soils

The effects of solution:soil ratio, major cations present in soils, and the ethylenediaminetetraacetic acid (EDTA):lead stoichiometric ratio on the extraction of lead using EDTA were studied for three different Superfund site soils, one rifle range soil, and one artificially lead-contaminated soil. Extraction of lead from the lead-contaminated soils was not affected by a solution:soil ratio as low as 3:1 but instead was dependent on the quantity of EDTA present. Results of the experiments showed that the extraction efficiencies were different for each soil. If sufficiently large amount of EDTA was applied (EDTA-Pb stoichiometric ratio greater than 10), most of the lead were extracted for all soils tested except for a Superfund site soil from a lead mining area. The differences in extraction efficiencies may be due to the major cations present in soils which may compete with lead for active sites on EDTA. For example, iron ions most probably competed strongly with lead for EDTA ligand sites for pH less than 6. In addition, copper and zinc may potentially compete with lead for EDTA ligand sites. Experimental results showed that addition of EDTA to the soil resulted in a very large increase in metals solubility. The total molar concentrations of major cations extracted were as much as 20 times the added molar concentration of EDTA. For some of the soils tested, lead may have been occluded in the iron oxides present in the soil which may affect lead extraction. While major cations present in the soil may be one of the factors affecting lead extraction efficiency, the type of lead species present also play a role.     

Lead Contamination of Urban Soils and Vegetation by Emissions from Secondary Lead Industries

The degree and extent of lead contamination of urban soils and vegetation in the vicinity of secondary lead industries are provided. These urban industries, a secondary smelter reprocessing lead from used batteries and scrap metal and a manufacturer of new storage batteries, were located near residential communities. Levels as high as 21,000 ppm of lead in the upper 5 cm of soil (based on air dried weight) and 3500 and 2700 ppm in willow foliage (not washed and washed, respectively, based on dry weight) were found adjacent to the secondary smelter, with the levels decreasing exponentially from the sources. The data on lead contamination of soils and vegetation at various distances and directions from the urban secondary lead industries were compared with levels of lead found in control urban and highway locations. In addition, arsenic levels in soil were examined as a tracer for the source of industrial lead emissions. High levels of lead found In both vegetation and soil in the vicinity of the urban industries reflected both historical and current emissions of lead in those areas. These studies were conducted for industrial abatement purposes; to assist medical related epidemiology studies; to define the areas of severe contamination for soil cleanup purposes; and to formulate guidelines for excessive levels of lead in soil and vegetation. Since lead in soil is persistent, concern arises with respect to pica for small children, contamination of edible vegetables grown in high-lead soil, and reentrainment of leaded particulate matter into the air.     

Lead sorption in calcareous soils

The sorption of lead by three soils that differed in texture and calcium carbonate content was studied at three different temperatures. Lead sorption was found to conform to both Freundlich and Langmuir isotherms. Soil adsorption maxima were derived from the reciprocal of the slope obtained by a least-squares fit of Langmuir plots for each soil. The highest adsorption capacity was exhibited by CaCO(3)-rich soil (773.55 mmol Pb kg(-1)). Raising the temperature from 298 K to 308 and 318 K increased the sorption capacity of all of the soils.     

Does Divergence of Nutrient Load Measurements Matter for Successful Mitigation of Marine Eutrophication?

Successful implementation of an international nutrient abatement agreement, such as the Baltic Sea Action Plan (BSAP), requires consistent understanding of the baseline nutrient loads, and a perception of acceptable costs and fairness in targeted reductions of these base line loads. This article presents a general framework for identifying the implications of divergence between different nutrient load quantification approaches, with regard to both cost and fairness criteria outcomes, for the international agreement to decrease nutrient loads into the Baltic Sea as presented in the BSAP. The results indicate that even relatively small divergence in the nutrient load quantification translates into relatively large differences in abatement cost for different Baltic Sea countries. A robust result, irrespective of differences in nutrient load assessments, is a conflict between abatement cost effectiveness and fairness, with relatively poor countries facing heavy abatement cost burdens for cost-effective international load abatement.     

Effects of acidic solutions on element dynamics in the monsoon evergreen broad-leaved forest at Dinghushan,China

BACKGROUND: Soil metal dynamics are affected by acid deposition. Little knowledge is available about the process in the lateritic soils under the monsoon forest in south China. METHODS: Samplings of Acmera acuminatissima, Cryptocarya concinna and Schima superba were grown from October, 2000 to July, 2002 in pots with a natural acid lateritic forest soil from Dinghushan. Pots were watered weekly with an acid solution (pH 3.05, 3.52, 4.00 or 4.40) or with tap water. Fe, Mn, Cu and Al were measured in soils, leachates and sapling leaves. RESULTS: Soil extractable Fe and leachate Al and Mn concentrations increased with a decreasing treatment pH. Soil reactive Al exhibited the opposite trend and decreased over time. The Ca/Al and Mg/ (Al+Mn) ratios did not decrease in the leaves of Schima superba, but decreased with a decreasing treatment pH for Cryptocaria concinna. Both ratios only decreased in the pH 3.05 treatment for Acmena CONCLUSIONS: Cu will not be toxic for plants since soil extractable Cu was not high and Fe will not be toxic either given that its root uptake was inhibited by Mn. Acid rains will lead to increased Mn and Al mobility in soil. Cryptocaria concinna will be the most sensible species to these changes (nutrient deficiency and direct Mn toxicity), while Schima superba should retain a good growth.     

Application of magnetite-activated persulfate oxidation for the degradation of PAHs in contaminated soils

In this study, feasibility of magnetite-activated persulfate oxidation (AP) was evaluated for the degradation of polycyclic aromatic hydrocarbons (PAHs) in batch slurry system. Persulfate oxidation activated with soluble Fe(II) (FP) or without activation (SP) was also tested. Kinetic oxidation of PAHs was tracked in spiked sand and in aged PAH contaminated soils at circumneutral pH. Quartz sand was spiked with: (i) single model pollutant (fluorenone) and (ii) organic extract isolated from two PAH contaminated soils (H and NM sampled from ancient coking plants) and was subjected to oxidation. Oxidation was also performed on real H and NM soils with and without an extraction pretreatment. Results indicate that oxidation of fluorenone resulted in its complete degradation by AP while abatement was very low (<20%) by SP or FP. In soil extracts spiked on sand, significant degradation of 16 PAHs was observed by AP (70-80%) in 1 week as compared to only 15% by SP or FP systems. But no PAH abatement was observed in real soils whatever the treatment used (AP, FP or SP). Then soils were subjected to an extraction pretreatment but without isolation of organic extract from soil. Oxidation of this pretreated soil showed significant abatement of PAHs by AP. On the other hand, very low degradation was achieved by FP or SP. Selective degradation of PAHs was observed by AP with lower degradation efficiency towards high molecular weight PAHs. Analyses revealed that no by-products were formed during oxidation. The results of this study demonstrate that magnetite can activate persulfate at circumneutral pH for an effective degradation of PAHs in soils. However, availability of PAHs and soil matrix were found to be the most critical factors for degradation efficiency.     

Biosurfactants during in situ bioremediation: factors that influence the production and challenges in evalution

Research on the influence of biosurfactants on the efficiency of in situ bioremediation of contaminated soil is continuously growing. Despite the constant progress in understanding the mechanisms involved in the effects of biosurfactants, there are still many factors that are not sufficiently elucidated. There is a lack of research on autochthonous or exogenous microbial metabolism when biostimulation or bioaugmentation is carried out to produce biosurfactants at contaminated sites. In addition, studies on the application of techniques that measure the biosurfactants produced in situ are needed. This is important because, although the positive influence of biosurfactants is often reported, there are also studies where no effect or negative effects have been observed. This review aimed to examine some studies on factors that can improve the production of biosurfactants in soils during in situ bioremediation. Moreover, this work reviews the methodologies that can be used for measuring the production of these biocomposts. We reviewed studies on the potential of biosurfactants to improve the bioremediation of hydrocarbons, as well as the limitations of methods for the production of these biomolecules by microorganisms in soil.     

Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.     

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.     

Effect of soil layering on NAPL removal behavior in soil-heated vapor extraction

Soil heating has been proposed as a method to enhance the vapor extraction of NAPLs from contaminated soils. Three-dimensional fluid flow and heat transfer simulations have been performed for soil-heated vapor extraction to determine the transient system performance for a hypothetical configuration. Soil layering has been considered in evaluation of the initial non-aqueous phase liquid (NAPL) distribution and in evaporation and transport to the vapor extraction location. Results from this layered model are compared with results for a homogeneous system with an initially uniform NAPL, indicating the influence of layering, the initial NAPL distribution, the type of NAPL, and the possibility of enhanced vapor diffusion. Not only is the NAPL removal time reduced significantly with the addition of heat, but the uncertainty in the removal time owing to a number of difficult to characterize in situ factors, such as layering and the initial NAPL distribution, is much less than for standard soil vapor extraction without heating, owing to the rise in temperature and increase in NAPL vapor pressure with time.     

The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity

To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTE’s) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTE’s only to a limited extent.The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe_ox) and to the reactivity of PTE’s in soils which in fact control the soluble fraction of the contaminants.The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTE’s in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils.     

Phytotoxicity of nickel in a range of European soils: influence of soil properties, Ni solubility and speciation

We investigated the influence of soil properties on Ni toxicity to barley root and tomato shoot growth, using 16 European soils. The effective concentration of added Ni causing 50% inhibition (EC(50)) ranged from 52 to 1929mgkg(-1) and from 17 to 920mgkg(-1) for the barley and tomato test, respectively, representing 37- and 54-fold variation among soils. Soil cation exchange capacity was the best single predictor for the EC(50). The EC(50) based on either the Ni concentration or free Ni(2+) activity in soil solution varied less among soils (7-14 fold) than that based on the total added Ni, suggesting that solubility of Ni is a key factor influencing its toxicity to plants. The EC(50) for free Ni(2+) activity from the barley test decreased with increasing pH, indicating a protective effect of protons. The results can be used in the risk assessment of Ni in the terrestrial environment.     

Field sampling of soil pore water to evaluate trace element mobility and associated environmental risk

Monitoring soil pollution is a key aspect in sustainable management of contaminated land but there is often debate over what should be monitored to assess ecological risk. Soil pore water, containing the most labile pollutant fraction in soils, can be easily collected in situ offering a routine way to monitor this risk. We present a compilation of data on concentration of trace elements (As, Cd, Cu, Pb, and Zn) in soil pore water collected in field conditions from a range of polluted and non-polluted soils in Spain and the UK during single and repeated monitoring, and propose a simple eco-toxicity test using this media. Sufficient pore water could be extracted for analysis both under semi-arid and temperate conditions, and eco-toxicity comparisons could be effectively made between polluted and non-polluted soils. We propose that in-situ pore water extraction could enhance the realism of risk assessment at some contaminated sites.     

Sorption of copper, zinc and lead on soil mineral phases

Soil mineral phases play a significant role in controlling heavy metal mobility in soils. The effective study of their relation needs the integrated use of several analytical methods. In this study, analytical electron microscopy analyses were combined with sequential chemical extractions on soils spiked with Cu, Zn and Pb. Our aims were to study the metal sorption capacity of soil mineral phases and the effect of presence of iron oxide and carbonate on this property of soil minerals. Copper and Pb were found to be characterized by higher and stronger sorption on the studied samples than Zn. Only the former two metals showed significant differences in their immobilized metal amounts on the studied samples and soil mineral particles. Highest metal amounts were sorbed on the swelling clay mineral particles (smectites and vermiculites), but iron-oxide phases may also have similar lead sorption capacity. Alkaline conditions due to the carbonate content of soils resulted both in increased sorption on the mineral particles for Cu and in enhanced role of precipitation for all the studied metals. On the other hand, the intimate association of phyllosilicates and iron resulted in significant increase in metal sorption capacity of the given particle. The results of sequential extractions could be successfully completed by the analytical electron microscopy analyses for studying the sorption capacity of discrete mineral particles. Their integrated use helps us in better understanding the heavy metal-mineral interactions in soils.     

Determination of the applicability of CERCLA's petroleum exclusion at contaminated sites – focus on metals

Areas impacted by petroleum refining and handling operations may become subject to CERCLA enforcement. Because of CERCLA's petroleum exclusion clause, determining whether contamination in a CERCLA Site originated from petroleum products or hazardous wastes becomes important. Because certain metals are typically enriched in wastes relative to petroleum products and background soils, knowledge of metal contents in these potential end member metal sources is an important step towards contaminant source identification in soils and sediments. In LNAPL plumes, metal content, particularly lead, may be claimed to be the result of wastes mishandling and not due only to the presence of leaded gasoline in the plume. Analysis of the percent gasoline in the plume and accounting for weathering are steps to determining whether the lead content in an LNAPL plume is within the historical lead concentration ranges in gasolines. In addition to metals analyses, understanding of operational parameters such as the history of petroleum refining and handling operations, leaks, spills, and cleanup activities are needed for successful conclusion of the applicability of the petroleum exclusion.