Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.     

Validation of the in vitro gastrointestinal (IVG) method to estimate relative bioavailable lead in contaminated soils

The effect of the dosing vehicle (e.g., dough) on the ability of an in vitro gastrointestinal (IVG) method to predict relative bioavailable Pb associated with soil ingestion was evaluated. Bioaccessible Pb determined by the IVG method was compared with relative bioavailable Pb measured from dosing trials using juvenile swine for 18 contaminated soils ranging from 1270 to 14200 mg Pb kg(-1). Bioaccessible Pb was measured in the IVG gastric extraction (GE) and intestinal extraction (IE) solutions. Mean bioaccessible Pb values were 32.2% for GE without dough, 23.0% for GE with dough, 1.06% for IE without dough, and 0.56% for IE with dough. It is possible that phytic acid associated with the dough addition decreased bioaccessible Pb. In vivo relative bioavailable Pb ranges for different swine tissues were 1 to 87% for blood, 0 to 110% for liver, 1 to 124% for kidney, and 0.04 to 94% for bone. Strong linear relationships between IVG GE Pb with dough (r > 0.76, P < 0.0002), IVG IE Pb with dough (r > 0.56, P < 0.015), and IVG GE Pb without dough (r > 0.81, P < 0.0001) and in vivo bioavailable Pb as estimated with blood, kidney, liver, and bone were found. Inexpensive in vitro methods may be useful in providing an estimate of the variability in relative bioavailable Pb at a single study site. The IVG method can be used to estimate relative bioavailable Pb, As, and Cd in contaminated soil.     

Trace element chemistry in residual-treated soil: key concepts and metal bioavailability

Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are important sinks for trace elements in soil-residual systems. The pH of the soil-residual system is often the most important chemical property governing trace element sorption, precipitation, solubility, and availability. Trace element phytoavailability in residual-treated soils is often estimated using soil extraction methods. However, spectroscopic studies show that sequential extraction methods may not be accurate in perturbed soil-residual systems. Plant bioassay is the best method to measure the effect of residuals on phytoavailability. Key concepts used to describe phytoavailability are (i) the salt effect, (ii) the plateau effect, and (iii) the soil-plant barrier. Metal availability in soil from metal-salt addition is greater than availability in soil from addition of metal-containing residuals. Plant metal content displays plateaus at high residual loadings corresponding to the residual's metal concentration and sorption capacity. The soil-plant barrier limits transmission of many trace elements through the food chain, although Cd (an important human health concern) can bypass the soil-plant barrier. Results from many studies that support these key concepts provide a basis of our understanding of the relationship between trace element chemistry and phytoavailability in residual-treated soils. Research is needed to (i) determine mechanisms for trace element retention of soil-residual systems, (ii) determine the effect of residuals on ecological receptors and the ability of residuals to reduce ecotoxicity in metal-contaminated soil, and (iii) predict the long-term bioavailability of trace elements in soil-residual systems.     

Partitioning species variability from soil property effects on phytotoxicity: ECx normalization using a plant contaminant sensitivity index

Soil properties mitigate hazardous effects of contaminants through soil chemical sequestration and should be considered when evaluating ecological risk from terrestrial contamination. Empirical models that quantify relationships between soil properties and toxicity to ecological receptors are necessary for site-specific adjustments to ecological risk assessments. However, differential sensitivities of test organisms in dose-response studies may limit the utility of such models. We present a novel approach to toxicity estimation that partitions the effect of differential sensitivities of test organisms from that of soil chemical/physical properties. Five soils that ranged in selected properties were spiked with five concentrations of sodium arsenate. Bioassays were conducted where above ground dry matter growth and the corresponding tissue arsenic concentrations were evaluated for three terrestrial plants (Alfalfa, Medicago sativa L.; Perennial ryegrass, Lolium perrene L.; and Japanese millet, Echinochloa crusgalli L.). Estimates were combined into a plant contaminant sensitivity index (PCSI) and used to normalize phytotoxicity parameters to the most sensitive species (i.e., alfalfa) where necessary. Simple linear regression and ANCOVA indicated a 36.5% increase in the explanatory power of the modifying effects of soil properties on phytotoxicity when differential arsenate sensitivities were accounted for by PCSI (r(2) = 0.477-0.833). Normalization of ecotoxicity parameters by PCSI is a seemingly effective approach to quantify the modifying effects of soil properties on phytotoxicity endpoints when it is of interest to consider multiple plant species (or varieties within a species) with differential sensitivities to experimental contaminants.     

Field test of in situ soil amendments at the Tar Creek National Priorities List Superfund site

A range of soil amendments including diammonium phosphate fertilizer (DAP), municipal biosolids (BS), biosolids compost, and Al- and Fe-based water treatment residuals were tested on Pb-, Zn-, and Cd-contaminated yard soils and tailings at the Tar Creek NPL site in Oklahoma to determine if amendments could restore a vegetative cover and reduce metal availability in situ. For the yard soils, all amendments reduced bioaccessible (assessed with a physiologic-based extraction method) Pb, with reductions ranging from 35% (BS+Al, DAP 0.5%, DAP+Compost+Al) to 57% (Compost+Al). Plant Zn (Cynadon dactylon L.) and NH4 NO3-extractable Cd and Zn were also reduced by a number of amendments. For the tailings, all amendments excluding BS reduced bioaccessible Pb, with the largest reductions observed in the DAP 3% and DAP3%+BS treatments (75 and 84%). Plant growth was suppressed in all treatments that contained DAP for the first season, with the highest growth in the treatments that included compost and biosolids. In the second year, growth was vigorous for all treatments. Plant Zn and Cd and extractable metal concentration were also reduced. A number of treatments were identified that reduced bioaccessible Pb and sustained a healthy plant with reduced metal concentrations. For the yard soil, Compost+Al was the most effective treatment tested. For the tailings, BS+DAP 1% was the most effective treatment tested. These results indicate that in situ amendments offer a remedial alternative for the Tar Creek site.     

Evaluation of chemical immobilization treatments for reducing heavy metal transport in a smelter-contaminated soil

Three chemical immobilization materials, agricultural limestone (AL), mineral rock phosphate (RP), and diammonium phosphate (DAP), were evaluated using solute transport experiments to determine their ability to reduce subsurface heavy metal transport in a smelter contaminated soil. Percent reductions in metals transported were based on comparison with cumulative totals of metal species eluted through 60 pore volumes from an untreated soil. Reductions of metal eluted from the AL treatment were 55% for Cd, 45.2% for Pb, and 21.9% for Zn. Rock phosphate mixed with soil at 60 and 180 g kg(-1) was generally ineffective for reducing Cd, Pb, and Zn elution with <27% reduction for Cd, Pb, and Zn. Rock phosphate placed under contaminated soil as a reactive barrier (i.e. layered RP) at 180 g kg(-1) reduced Cd 53% and Zn 24%, and was the most efficient treatment for reducing Pb (99.9%) transport. DAP treatments were superior to all other materials for reducing Cd and Zn elution with reduction >77% for Zn and >91% for Cd from the 90 g DAP kg(-1) treatment. Increasing DAP from 10 to 90 g kg(-1) increased total arsenic released from 0.13 to 29.5 mg kg(-1) and total P eluted from 2.31 to 335 mg. DAP at 10 g kg(-1) was the most effective treatment for immobilizing the combination of Cd, Pb, and Zn, with reductions of 94.6, 98.9, and 95.8%, respectively.     

Use of drinking water treatment residuals as a potential best management practice to reduce phosphorus risk index scores

The P risk index system has been developed to identify agricultural fields vulnerable to P loss as a step toward protecting surface water. Because of their high Langmuir phosphorus adsorption maxima (P(max)), use of drinking water treatment residuals (WTRs) should be considered as a best management practice (BMP) to lower P risk index scores. This work discusses three WTR application methods that can be used to reduce P risk scores: (i) enhanced buffer strip, (ii) incorporation into a high soil test phosphorus (STP) soil, and (iii) co-blending with manure or biosolids. The relationship between WTR P(max) and reduction in P extractability and runoff P was investigated. In a simulated rainfall experiment, using a buffer strip enhanced with 20 Mg WTR ha(-1), runoff P was reduced by from 66.8 to 86.2% and reductions were related to the WTR P(max). When 25 g kg(-1) WTR was incorporated into a high STP soil of 315 mg kg(-1) determined using Mehlich-3 extraction, 0.01 M calcium chloride-extractable phosphorus (CaCl(2)-P) reductions ranged from 60.9 to 96.0% and were strongly (P < 0.01) related to WTR P(max). At a 100 g kg(-1) WTR addition, Mehlich 3-extractable P reductions ranged from 41.1 to 86.7% and were strongly (P < 0.01) related to WTR P(max). Co-blending WTR at 250 g kg(-1) to manure or biosolids reduced CaCl(2)-P by >75%. The WTR P(max) normalized across WTR application rates (P(max) x WTR application) was significantly related to reductions in CaCl(2)-P or STP. Using WTR as a P risk index modifying factor will promote effective use of WTR as a BMP to reduce P loss from agricultural land.     

Evaluation of some organic-based biopolymers as green inhibitors for calcium sulfate scales

This study focused on using scale inhibitors for calcium sulfate that are not only highly effective, but also comply with present restrictive environmental control legislations. In this respect, some biodegradable compounds-based biopolymers, such as carboxymethyl starch (CMS), carboxymethyl cellulose (CMC), and chitosan (Ch), were evaluated at temperatures 90–95 and 130°C. The results obtained were compared with the performance of polyaspartic acid (PAA), which is well known in this application, as well as other chelating synthetic polymers (polyacrylamide and amphoteric polyacrylamide). The role of the degree of substitution (DS) of carboxymethylated biopolymer and the charge density of polyacrylamide (AmPAM-30 and AmPAM-50) on inhibition performance of scale were also examined. The synergistic effect of PAA with investigated inhibitors was studied for economic and environmental purposes. The results revealed that both the degree of substitution of carboxymethylated biopolymers and charge density of polyacrylamide have a profound effect on improving the performance of the investigated scale inhibitors. The efficiency values were correlated to the thermal degradation behavior (TGA) of biopolymers. PAA had the highest synergistic effect of all investigated inhibitors, where the inhibition efficiency was found to range from 98% to 100%, at a temperature of 130°C, with low doses of both PAA (2 ppm) together with biopolymers. This efficiency is observed using 20–40 ppm of PAA. The synergistic effect of PAA (2 ppm) also showed enhancement of the performance of low doses of polyacrylamides (5 ppm) in maintaining soluble Ca²⁺ in solutions, increasing the efficiency from ∼57% to ∼100%, as well as its ecotoxicological property.