Effectiveness of amendments on re-acidification and heavy metal immobilization in an extremely acidic mine soil

Previous studies have shown that the application of soil amendments is efficient in reducing acidity and heavy metal bioavailability in mine soils. However, it remains a challenge for environmentalists to predict accurately and control economically the re-acidification in re-vegetated mine soils. In this study, net acid generation (NAG) test and bioassay technique were employed to assess the effectiveness of the amendments [including lime, N-P-K (nitrogen, phosphorous and potassium) fertilizer, phosphate and river sediment] on re-acidification and heavy metal immobilization in an extremely acid (pH < 3) mine soil. Our results suggested that NAG test was a rapid and accurate approach to assess the effectiveness of the amendments on re-acidification potential of the mine soil. Interestingly, it was found that phosphate and river sediment played quite specific roles in preventing the re-acidification in the mine soil. In addition, the results also indicated that the addition of 25 t ha(-1) lime combined with river sediment (30%) might be an economical method to successfully control the acidification and re-acidification in the extremely acid mine soil, allowing the re-establishment of the plants. Collectively, our results implied that the combined use of NAG test and bioassay assessment was effective in evaluating a reclamation strategy for extremely acidic mine soils.     

Metal immobilization and phosphorus leaching after stabilization of pyrite ash contaminated soil by phosphate amendments

In this study we would like to show the importance of a holistic approach to evaluation of chemical stabilization using phosphate amendments. An extensive evaluation of metal stabilization in contaminated soil and an evaluation of the leaching of phosphorus induced after treatment were performed. The soil was highly contaminated with Cu (2894 mg kg(-1)), Zn (3884 mg kg(-1)), As (247 mg kg(-1)), Cd (12.6 mg kg(-1)) and Pb (3154 mg kg(-1)). To immobilize the metals, mixtures of soil with phosphate (from H(3)PO(4) and hydroxyapatite (HA) with varying ratios) were prepared with a constant Pb : P molar ratio of 1: 10. The acetic acid extractable concentration of Pb in the mixture with the highest amount of added phosphoric acid (n(H(3)PO(4)) : n(HA) = 3 : 1) was reduced to 1.9% (0.62 mg L(-1)) of the extractable Pb concentration in the untreated soil, but the content of water extractable phosphorus in the samples increased from 0.04 mg L(-1) in the untreated soil sample up to 14.3 mg L(-1) in the same n(H(3)PO(4)) : n(HA) = 3 : 1 mixture. The high increase in arsenic mobility was also observed after phosphate addition. The PBET test showed phosphate induced reduction in Pb bioavailability. In attempting to stabilize Pb in the soil with the minimum treatment-induced leaching of phosphorus, it was found that a mixture of soil with phosphate addition in the molar ratio of H(3)PO(4) : HA of 0.75 : 1 showed the most promising results, with an acetic acid extractable Pb concentration of 1.35 mg L(-1) and a water extractable phosphorus concentration of 1.76 mg L(-1). The time-dependent leaching characteristics of metals and phosphorus for this mixture were evaluated by a column experiment, where irrigation of the soil mixture with the average annual amount of precipitation in Slovenia (1000 mm) was simulated. The phosphorus concentration in the leachates decreased from 2.60 mg L(-1) at the beginning of irrigation to 1.00 mg L(-1) at the end.     

Impacts of epigeic, anecic and endogeic earthworms on metal and metalloid mobility and availability

The introduction of earthworms into soils contaminated with metals and metalloids has been suggested to aid restoration practices. Eisenia veneta (epigeic), Lumbricus terrestris (anecic) and Allolobophora chlorotica (endogeic) earthworms were cultivated in columns containing 900 g soil with 1130, 345, 113 and 131 mg kg(-1) of As, Cu, Pb and Zn, respectively, for up to 112 days, in parallel with earthworm-free columns. Leachate was produced by pouring water on the soil surface to saturate the soil and generate downflow. Ryegrass was grown on the top of columns to assess metal uptake into biota. Different ecological groups affected metals in the same way by increasing concentrations and free ion activities in leachate, but anecic L. terrestris had the greatest effect by increasing leachate concentrations of As by 267%, Cu by 393%, Pb by 190%, and Zn by 429% compared to earthworm-free columns. Ryegrass grown in earthworm-bearing soil accumulated more metal and the soil microbial community exhibited greater stress. Results are consistent with earthworm enhanced degradation of organic matter leading to release of organically bound elements. The degradation of organic matter also releases organic acids which decrease the soil pH. The earthworms do not appear to carry out a unique process, but increase the rate of a process that is already occurring. The impact of earthworms on metal mobility and availability should therefore be considered when inoculating earthworms into contaminated soils as new pathways to receptors may be created or the flow of metals and metalloids to receptors may be elevated.     

典型重金属污染农田能源植物示范种植研究

为探索安全经济利用重金属中度-重度污染农田的模式,在浙江某典型重金属复合污染农田开展了能源植物(甜高粱Sweet sorghum、甘蔗Saccharum sinensisRoxb.、香根草Vetiveria和盐肤木Rhus chinensis)种植示范研究.结果表明,经施加0.1%的石灰和0.2%的磷矿粉改良后,土壤p...     

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.     

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.     

Survey and evaluation of contaminants in earthworms and in soils derived from dredged material at confined disposal facilities in the Great Lakes Region

Soils derived from dredged material were collected, together with earthworms from nine confined disposal facilities located in the Great Lakes Region. These samples were analyzed for 18 elements, 11 organochlorine pesticides, PCBs, and 24 polycyclic aromatic hydrocarbons. The concentrations detected in earthworms were evaluated in terms of their potential hazard to wildlife, which for the sake of the evaluation were assumed to prey entirely either on earthworms or on other soil invertebrates having similar concentrations. The soil concentrations (dry wt.) of the contaminants of greatest concern were <1.9 to 32 ppm Cd, <0.053 to 0.94 ppm Hg, 4.6 to 550 ppm Pb, and <0.1 to 1.0 ppm PCBs. The concentrations in earthworms (dry wt., ingested soil included) were as high as 91 ppm Cd, 1.6 ppm Hg, 200 ppm Pb, and 1.8 ppm PCBs. Based on laboratory toxicity studies of relatively sensitive species, and on concentration factors calculated from the earthworm and soil data, we estimated that lethal or serious sublethal effects on wildlife might be expected at concentrations of 10 ppm Cd, 3 ppm Hg, 670 ppm Pb, and 1.7 ppm PCBs in alkaline surface soils derived from dredged material. Concentrations of polycyclic aromatic hydrocarbons in earthworms were well below those in soil.     

Environmental hazard of cadmium, copper, lead and zinc in metal-contaminated soils remediated by sulfosuccinamate formulation

Accumulation of metals in soil at elevated concentrations causes risks to the environmental quality and human health for more than one hundred million people globally. The rate of metal release and the alteration of metal distribution in soil phases after soil washing with a sulfosuccinamate surfactant solution (Aerosol 22) were evaluated for four contaminated soils. Furthermore, a sequential extraction scheme was carried out using selective extractants (HAcO, NH(2)OH·HCl, H(2)O(2) + NH(4)AcO) to evaluate which metal species are extracted by A22 and the alteration in metal distribution upon surfactant-washing. Efficiency of A22 to remove metals varied among soils. The washing treatment released up to 50% of Cd, 40% of Cu, 20% of Pb and 12% of Zn, mainly from the soluble and reducible soil fractions, therefore, greatly reducing the fraction of metals readily available in soil. Metal speciation analysis for the solutions collected upon soil washing with Aerosol 22 further confirmed these results. Copper and lead in solution were mostly present as soluble complexes, while Cd and Zn were present as free ions. Besides, redistribution of metals in soil was observed upon washing. The ratios of Zn strongly retained in the soil matrix and Cd complexed with organic ligands increased. Lead was mobilized to more weakly retained forms, which indicates a high bioavailability of the remaining Pb in soil after washing. Comprehensive knowledge on chemical forms of metals present in soil allows a feasible assessment of the environmental impact of metals for a given scenario, as well as possible alteration of environmental conditions, and a valuable prediction for potential leaching and groundwater contamination.     

Fractionation and elemental association of Zn, Cd and Pb in soils contaminated by Zn minings using a continuous-flow sequential extraction

Fractionation and elemental association of Zn, Cd, and Pb in soils near Zn mining areas were studied using a continuous-flow sequential extraction approach. The recently developed sequential extraction procedure not only gave fractional distribution data for evaluation of the mobility or potential environmental impact of the metals, but also the extraction profiles (extractograms) which were used for study of elemental association. In addition, the elemental atomic ratio plot extractogram can be used to demonstrate the degree of anthropogenic contamination. Seventy-nine soil samples were collected in the vicinity of a Zn mine and were fractionated into 4 phases i.e. exchangeable (F1), acid soluble (F2), reducible (F3) and oxidizable (F4) phases. Most samples were contaminated with Zn, Cd and Pb. The reducible phase is the most abundant fraction for Zn and Pb (>50%) while Cd is concentrated in the first 3 extraction steps. The distribution patterns of Cd were obviously affected by soil pH. 55% of Cd appears predominantly in the F1 fraction for acidic soils while in neutral and alkaline soils, it was mostly (70%) found in the F2 + F3 fractions. The extractograms obtained from the continuous-flow extraction system revealed close association between Zn, Cd, Pb and Fe in the acid soluble phase, Cd-Pb and Zn-Fe in the reducible phase for contaminated soils. A correlation study of the 3 metals using a correlation coefficient was also performed to compare the results with the elemental association revealed by the extractograms. Atomic ratio plot extractograms of Zn/Fe, Cd/Fe and Pb/Fe in the reducible phase, where contaminated metals are predominant, can be used to evaluate the degree of anthropogenic contamination. From the elemental atomic ratio plot, it is obvious that the contaminants Cd and Pb are mostly adsorbed on the surface of Fe oxides. Zn, which is present in an approximately 1 ratio 1 ratio with Fe in contaminated soils, does not show a similar trend to that found for Cd and Pb.     

Toxicity assessment for petroleum-contaminated soil using terrestrial invertebrates and plant bioassays

The assessment of soil quality after a chemical or oil spill and/or remediation effort may be measured by evaluating the toxicity of soil organisms. To enhance our understanding of the soil quality resulting from laboratory and oil field spill remediation, we assessed toxicity levels by using earthworms and springtails testing and plant growth experiments. Total petroleum hydrocarbons (TPH)-contaminated soil samples were collected from an oilfield in Sfax, Tunisia. Two types of bioassays were performed. The first assessed the toxicity of spiked crude oil (API gravity 32) in Organization for Economic Co-operation and Development artificial soil. The second evaluated the habitat function through the avoidance responses of earthworms and springtails and the ability of Avena sativa to grow in TPH-contaminated soils diluted with farmland soil. The EC₅₀ of petroleum-contaminated soil for earthworms was 644 mg of TPH/kg of soil at 14 days, with 67 % of the earthworms dying after 14 days when the TPH content reached 1,000 mg/kg. The average germination rate, calculated 8 days after sowing, varied between 64 and 74 % in low contaminated soils and less than 50 % in highly contaminated soils.     

Leaching Characteristics of Arsenic and Heavy Metals in Urban Roadside Soils Using a Simple Bioavailability Extraction Test

Regular ingestion of soils could pose a potential health threat due to long-term toxic element exposure. In order to estimate the human bioavailability quotients for As and heavy metals, 12 urban roadside soil samples were collected and analyzed for As, Pb, Cu, Zn, Ni, Co, and Cr using Simple Bioavailability Extraction Test (SBET). The quantities of As, Pb, Cu, Zn, Ni, Co, and Cr leached from soils within the simulated human stomach for 1 h indicated, on average, 27.3, 71.7, 40.4, 59.3, 17.7, 27.2 and 5.6% bioavailability, respectively. Significant positive correlations were observed between the amounts leached using SBET and the total amounts dissolved with HNO₃-HCl-HF acid mixtures. Stepwise multiple regression analysis indicated that the amounts leached with SBET for As, Pb, Zn, Ni, and Co were not related to any of the physic-chemical parameters measured (i.e., soil texture, pH, total organic matter). These results may be valuable for providing input data for risk assessment at sites subject to anthropogenic soil contamination.     

Effects of soil amendments on the bioavailability of heavy metals from zinc mine tailings

A study was conducted to test the effects of soil amendments on the bioavailability of heavy metals in a zinc mine tailings containing soil to plants, using the Indian mustard plant (Brassica juncea) as a test organism. Zinc mine tailing containing soil was amended with humus soil (HS) and phosphatic clay (PC). The zinc mine tailing containing soil (ZMTS) was characterized for heavy metals. It was mixed with PC and HS, and four mixtures were prepared. The first mixture contained ZMTS, and served as a control. The second mixture contained ZMTS and PC in the ratio of 1:1 (w/w). The third mixture contained ZMTS and HS in the ratio of 1:1(w/w). The fourth mixture containing ZMTS, PC and HS in the ratio of (2:1:1) (w/w). A slight increase in the bioavailability of Pb, Cu, Zn and Mn was noticed with increase in the incubation time from 14 to 42 days. The bioavailability of Pb, Cu, Zn and Mn from ZMTS alone in Brassica plant was in the range of 94-99% up to 42 days. Addition of PC and HS to the ZMTS soil reduced the bioavailabilities of Pb by (15%), of Cu by (20%), of Zn by (20%) and of Mn by (25%) in the mustard plant. The data showed that PC in the presence of HS had a high affinity for the heavy metals in the order of Pb, Cu, Zn and Mn.     

A survey of Pb,Cu, Zn,Cd, Cr,As, and Se in earthworms and soil from diverse sites

Earthworms and soils were collected from 20 diverse sites in Maryland, Pennsylvania, and Virginia, and were analyzed for Pb, Cu, Zn, Cd, Cr, As, and Se. Correlation coefficients relating concentrations of the elements in earthworms to concentrations in soil were low (–0.20<r<+0.57). Species differences and ecological variables contributed to the variability in concentrations of these elements in earthworms. The maximum concentrations of Pb (2100 ppm), Zn (1600 ppm), Cd (23 ppm) and Se (7.6 ppm) detected in earthworms were in the range reported to be toxic to animals fed diets containing these elements; however, even in the absence of any environmental contamination, some species of earthworms may contain high concentrations of Pb, Zn, and Se. Earthworms of the genus Eisenoides, for example, were exceptional in their ability to concentrate Pb. When earthworms are used as indicators of environmental contamination, it is important to identify the species, to report the soil characteristics, and to collect similar earthworms from very similar but uncontaminated soil.     

Bio-accumulation and distribution of heavy metals in black mustard (Brassica nigra Koch)

There has been carried out a comparative research, which to allow us to determine the quantities and the depots of accumulation of Pb, Cu, Zn and Cd in the vegetative and reproductive organs of Brassica nigra, as well as to identify the possibilities of growing on soils, contaminated by heavy metals and its use for the purposes of the phytoremeditation. Experiments have been implemented in field and in controlled conditions. B. nigra is tolerant towards the heavy metals and could be successfully grown in regions of low and moderate level of contamination with heavy metals, without lowering of the quantity and quality of the manufactured production. The depots for accumulation, in case it is being grown on contaminated soils without Cu follows the order: roots > fruit's shells > stems > seeds. In the case of its growing on non-contaminated soils the order roots > fruit's shells > seeds > stems preserves for the Pb, while the order for the Cu, Zn, and Cd is: fruit's shells > seeds > stems > roots. A relation is determined between the quantity of the total and the mobile forms of metals on one hand, and their total quantity in the plants in the field, as well as, in the pot experiments, on the other. A drastic exclusion is made by the Pb in the pot experiments, as its basic part is blocked in compounds that are hardly soluble. Its absorption by the plants is almost entirely blocked, which is almost a degree lower than that obtained in the field experiments and is commensurable with the results obtained in non-contaminated soils. Clarification of the reasons causing this effect requires additional examinations and above all, fractionation of the soil and determination of the forms and depots of localization of Pb compounds.     

Availability and Assessment of Fixing Additives for The in Situ Remediation of Heavy Metal Contaminated Soils: A Review

The use of low-cost and environmental safety amendments for the in situ immobilization of heavy metals has been investigated as a promising method for contaminated soil remediation. Natural materials and waste products from certain industries with high captive capacity of heavy metals can be obtained and employed. Reduction of extractable metal concentration and phytotoxicity could be evaluated and demonstrated by the feasibility of various amendments in fixing remediation. In this review, an extensive list of references has been compiled to provide a summary of information on a wide range of potentially amendment resources, including organic, inorganic and combined organic-inorganic materials. The assessment based on the economic efficiency and environmental risks brought forth the potential application values and future development directions of this method on solving the soil contamination.     

Petroleum contaminated soil in Oman: Evaluation of bioremediation treatment and potential for reuse in hot asphalt mix concrete

This paper presents a study that aims at evaluating the leaching characteristics of petroleum contaminated soils as well as their application in hot mix asphalt concrete. Soil samples are environmentally characterized in terms of their total heavy metals and hydrocarbon compounds and leachability. The total petroleum hydrocarbon (TPH) present in the PCS before and after treatment was determined to be 6.8% and 5.3% by dry weight, indicating a reduction of 1% in the TPH of PCS due to the current treatment employed. Results of the total heavy metal analysis on soils indicate that the concentrations of heavy metals are lower when extraction of the soil samples is carried out using hexane in comparison to TCE. The results show that the clean soils present in the vicinity of contaminated sites contain heavy metals in the following decreasing order: nickel (Ni), followed by chromium (Cr), zinc (Zn), copper (Cu), lead (Pb), and vanadium (V). The current treatment practice employed for remediation of the contaminated soil reduces the concentrations of nickel and chromium, but increases the concentrations of all remaining heavy metals.     

Lead contamination of an agricultural soil in the vicinity of a shooting range

In this study, coupled Pb concentration/Pb isotope data were used to evaluate the effect of a shooting range (operational for over 30 years) on Pb contamination of adjacent agricultural soils and the associated environmental risks. Lead was mainly concentrated in the arable layer of the contaminated agricultural soils at total concentrations ranging from 573 to 694 mg kg^???1. Isotopic analyses (²⁰⁶Pb/²⁰⁷Pb) proved that Pb originated predominantly from the currently used pellets. Chemical fractionation analyses showed that Pb was mainly associated with the reducible fraction of the contaminated soil, which is in accordance with its predominant soil phases (PbO, PbCO₃). The 0.05 M EDTA extraction showed that up to 62% of total Pb from the contaminated site is potentially mobilizable. Furthermore, Pb concentrations obtained from the synthetic precipitation leaching procedure extraction exceeded the regulatory limit set by the United States Environmental Protection Agency for drinking water. Ion exchange resin bags showed to be inefficient for determining the vertical distribution of free Pb^2?+? throughout the soil profile. Increased Pb concentrations were found in the biomass of spring barley (Hordeum vulgare L.) sampled at the studied site and two possible pathways of Pb uptake have been identified: (1) through passive diffusion-driven uptake by roots and (2) especially through atmospheric deposition, which was also proved by analyses of a bioindicator species (bryophyte Hypnum cupressiforme Hedw.). This study showed that shooting ranges can present an important source of Pb contamination of agricultural soils located in their close vicinity.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

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.     

Evaluating the Applicability of Regulatory Leaching Tests for Assessing Lead Leachability in Contaminated Shooting Range Soils

The toxicity characteristic leaching procedure (TCLP) is the current US-EPA standard protocol to evaluate metal leachability in wastes and contaminated soils. However, application of TCLP to assess lead (Pb) leachability from contaminated shooting range soils may be questionable. This study determined Pb leachability in the range soils using TCLP and another US-EPA regulatory leaching method, synthetic precipitation leaching procedure (SPLP). Possible mechanisms that are responsible for Pb leaching in each leaching protocol were elucidated via X-ray diffraction (XRD). Soil samples were collected from the backstop berms at four shooting ranges, with Pb concentrations ranging from 5,000 to 60,600 mg kg⁻¹ soil. Lead concentrations in the TCLP leachates were from 3 to 350 mg l⁻¹, with all but one soil exceeding the USEPA non-hazardous waste disposal limit of 5 mg l⁻¹. However, continued dissolution of metallic Pb particles from spent Pb bullets and its re-precipitation as cerussite (PbCO₃) prevented the TCLP extraction from reaching equilibrium at the end of the standard leaching period (18 h). Thus, the standard one-point TCLP test would either over- or under-estimate Pb leachability in shooting range soils. Lead concentration in the SPLP leachates ranged from 0.021 to 2.6 mg l⁻¹, with all soils above the USEPA regulatory limit of 0.015 mg l⁻¹. In contrast to TCLP, SPLP leaching had reached equilibrium, with regard to both pH and Pb concentrations, within the standard 18 h leaching period, and the analytical SPLP results were in good agreement with those derived from modeling. Thus, we concluded that SPLP is a more appropriate alternative than TCLP for assessing lead leachability in range soils.