Ganga M. Hettiarachchi

In Situ Stabilization of Soil Lead Using Phosphorus and Manganese Oxide

In situ stabilization of Pb contaminated soils can be accomplished by adding P and Mn(IV) oxide. However, the long-term efficacy of in situ stabilization under continual P removal through plant growth is unknown. Moreover, the effects these treatments have on phytoavailability of other metals (Cd and Zn) commonly associated with Pb in soil are not well understood. Greenhouse experiments using sudax [Sorghum vulgare (L.) Moench] and Swiss chard [Beta vulgaris (L.) Koch] were carried out to evaluate the effects of plant growth on soil Pb bioavailability to humans after addition of P and other amendments, and the effects of these treatments on Pb, Cd, and Zn phytoavailability in three metal-contaminated soils. Eight treatments were used: zero P; 2500 mg of P as triple superphosphate (TSP); 5000 mg of P as TSP or phosphate rock (PR); 5000 mg of Mn oxide/kg; and combinations of Mn oxide and P as TSP or PR. The addition of P and/or Mn oxide significantly reduced bioavailable Pb, as measured by the physiologically based extraction test (PBET), in soils compared with the control even after extensive cropping. The PBET data also suggested that removal of P from soluble P sources by plants could negate the beneficial effects of P on bioavailable Pb, unless sufficient soluble P was added or soluble P was combined with Mn oxide. In general, Ph, Cd, and Zn concentrations in shoot tissues of sudax and Swiss chard were reduced significantly by TSP and did not change with the addition of PR. The combination of PR and Mn oxide significantly reduced Pb concentrations in plants compared with the control.

Dissolution kinetics of macronutrient fertilizers coated with manufactured zinc oxide nanoparticles.

The solubility of Zn in Zn fertilizers plays an important role in the agronomic effectiveness of the fertilizer. On the basis of thermodynamics, zinc oxide (ZnO) nanoparticles (NPs) should dissolve faster and to a greater extent than bulk ZnO particles (equivalent spherical diameter >100 nm). These novel solubility features of ZnO NPs might be exploited to improve the efficiency of Zn fertilizers. In this study, we compared the Zn solubility and dissolution kinetics of ZnO nanoparticles and bulk ZnO particles coated onto two selected granular macronutrient fertilizers, urea and monoammonium phosphate (MAP). The main Zn species on coated MAP and urea granules were zinc ammonium phosphate and ZnO, respectively. Coated MAP granules showed greater Zn solubility and faster dissolution rates in sand columns compared to coated urea granules, which may be related to pH differences in the solution surrounding the fertilizer granules. The kinetics of Zn dissolution was not affected by the size of the ZnO particles applied for coating of either fertilizer type, possibly because solubility was controlled by formation of the same compounds irrespective of the size of the original ZnO particles used for coating.

Effects of Phosphorus Additions on Lead, Cadmium, and Zinc Bioavailabilities in a Metal-Contaminated Soil

The use of phosphorus (P) to reduce lead (Pb)bioavailability is being proposed as an alternative to excavationand disposal as a remedial technology for Pb-contaminated soilsin residential areas. The objective of this study was todetermine the influence of P sources and rates andCaCO3additions on the bioavailabilities of Pb, cadmium (Cd), and zinc(Zn) in a contaminated soil material using plants, a sequentialextraction procedure, and ion activities in equilibrium solutionas indicators. A contaminated soil containing 370 mg kg-1 Cd, 2800 mg kg-1 Pb and 29100 mg kg-1 Zn was amended ina factorial arrangement of CaCO3 (0 or 2000 mg kg-1) and P as rock phosphate or KH2PO4 at 0:1, 2:1 or 4:1P:Pb mole ratios. A pot study was conducted using sorghum-sudangrass (Sorghum bicolor L. Moench). The addition of P did not influence Pb concentrations in plant tissue and had little effect on Cd concentrations. An interaction between P source and level of P addition was found for Zn concentrations in plant tissue; concentrations increased with increasing amounts of P from KH2PO4 anddecreased with increasing amounts of P from rock phosphate. Sequential extraction results suggested a much greater reduction in Pb bioavailability from treatment withKH2PO4 than with rock phosphate and that P influencedthe fractionations of Cd and Zn. Activities of Cd2+,Pb2+, and Zn2+ in equilibrium solutions generally weredecreased by rock phosphate and increased by KH2PO4. Saturation indices suggested the addition ofKH2PO4shifted the soil equilibrium from octavite to hydroxypyromorphite, whereas solid-phase control of Cd2+ andZn2+ was not influenced by soil amendments. A soluble Psource was more effective in reducing Pb bioavailability thanrock phosphate but had variable effects on Cd and Znbioavailabilities.

Field evaluations on soil plant transfer of lead from an urban garden soil

Lead (Pb) is one of the most common contaminants in urban soils. Gardening in contaminated soils can result in Pb transfer from soil to humans through vegetable consumption and unintentional direct soil ingestion. A field experiment was conducted in 2009 and 2010 in a community urban garden with a soil total Pb concentration of 60 to 300 mg kg. The objectives of this study were to evaluate soil-plant transfer of Pb, the effects of incorporation of a leaf compost as a means of reducing Pb concentrations in vegetables and the bioaccessibility of soil Pb, and the effects of vegetable cleaning techniques on the Pb concentrations in the edible portions of vegetables. The amount of compost added was 28 kg m. The tested plants were Swiss chard, tomato, sweet potato, and carrots. The vegetable cleaning techniques were kitchen cleaning, laboratory cleaning, and peeling. Compost addition diluted soil total Pb concentration by 29 to 52%. Lead concentrations of the edible portions of vegetables, except carrot, were below the maximum allowable limits of Pb established by the Food and Agriculture Organization and the World Health Organization. Swiss chard and tomatoes subjected to kitchen cleaning had higher Pb concentrations than laboratory-cleaned plants. Cleaning methods did not affect Pb concentrations in carrots. Bioaccessible Pb in the compost-added soils was 20 to 30% less than that of the no-compost soils; compost addition reduced the potential of transferring soil Pb to humans via vegetable consumption and direct soil ingestion. Thorough cleaning of vegetables further reduced the potential of transferring soil Pb to humans.

Bioavailability-Based In Situ Remediation To Meet Future Lead (Pb) Standards in Urban Soils and Gardens

Recently the Centers for Disease Control and Prevention lowered the blood Pb reference value to 5 μg/dL. The lower reference value combined with increased repurposing of postindustrial lands are heightening concerns and driving interest in reducing soil Pb exposures. As a result, regulatory decision makers may lower residential soil screening levels (SSLs), used in setting Pb cleanup levels, to levels that may be difficult to achieve, especially in urban areas. This paper discusses challenges in remediation and bioavailability assessments of Pb in urban soils in the context of lower SSLs and identifies research needs to better address those challenges. Although in situ remediation with phosphate amendments is a viable option, the scope of the problem and conditions in urban settings may necessitate that SSLs be based on bioavailable rather than total Pb concentrations. However, variability in soil composition can influence bioavailability testing and soil amendment effectiveness. More data are urgently needed to better understand this variability and increase confidence in using these approaches in risk-based decision making, particularly in urban areas.

Lead in Urban Soils: A Real or Perceived Concern for Urban Agriculture?

Urban agriculture is growing in cities across the United States. It has the potential to provide multiple benefits, including increased food security. Concerns about soil contamination in urban areas can be an impediment to urban agriculture. Lead is the most common contaminant in urban areas. In this paper, direct (soil ingestion via outdoor and indoor exposure) and indirect (consumption of food grown in Pb-contaminated soils) exposure pathways are reviewed. It is highly unlikely that urban agriculture will increase incidences of elevated blood Pb for children in urban areas. This is due to the high likelihood that agriculture will improve soils in urban areas, resulting in reduced bioavailability of soil Pb and reduced fugitive dust. Plant uptake of Pb is also typically very low. The exceptions are low-growing leafy crops where soil-splash particle contamination is more likely and expanded hypocotyl root vegetables (e.g., carrot). However, even with higher bioaccumulation factors, it is not clear that the Pb in root vegetables or any other crops will be absorbed after eating. Studies have shown limited absorption of Pb when ingested with food. Best management practices to assure minimal potential for exposure are also common practices in urban gardens. These include the use of residuals-based composts and soil amendments and attention to keeping soil out of homes. This review suggests that benefits associated with urban agriculture far outweigh any risks posed by elevated soil Pb.

Root Uptake of Lipophilic Zinc-Rhamnolipid Complexes

This study investigated the formation and plant uptake of lipophilic metal-rhamnolipid complexes. Monorhamnosyl and dirhamnosyl rhamnolipids formed lipophilic complexes with copper (Cu), manganese (Mn), and zinc (Zn). Rhamnolipids significantly increased Zn absorption by Brassica napus var. Pinnacle roots in (65)Zn-spiked ice-cold solutions, compared with ZnSO4 alone. Therefore, rhamnolipid appeared to facilitate Zn absorption via a nonmetabolically mediated pathway. Synchrotron XRF and XAS showed that Zn was present in roots as Zn-phytate-like compounds when roots were treated with Zn-free solutions, ZnSO4, or Zn-EDTA. With rhamnolipid application, Zn was predominantly found in roots as the Zn-rhamnolipid complex. When applied to a calcareous soil, rhamnolipids increased dry matter production and Zn concentrations in durum (Triticum durum L. cv. Balcali-2000) and bread wheat (Triticum aestivum L. cv. BDME-10) shoots. Rhamnolipids either increased total plant uptake of Zn from the soil or increased Zn translocation by reducing the prevalence of insoluble Zn-phytate-like compounds in roots.

Safety of gardening on lead- and arsenic-contaminated urban brownfields

Elevated levels of lead (Pb) and arsenic (As) are not uncommon for urban soils. Test plots were established at urban gardens in Tacoma and Seattle, WA. The Tacoma site was contaminated with Pb (51-312 mg kg) and As (39-146 mg kg), and the Seattle site had high Pb soil concentrations ranging from 506 to 2022 mg kg and As concentrations of <20 mg kg. The efficacy of biosolids mix and compost amendment in reducing Pb and As concentrations in three vegetables (carrots, lettuce, and tomatoes) and the bioaccessibility of soil Pb and As were evaluated. Food-chain transfer of Pb and As were evaluated by measuring plant Pb and As concentrations after kitchen-style washing, a laboratory cleaning procedure, or peeling. The experimental design was a randomized complete block with a split-plot arrangement. Tacoma site treatments included a Class A biosolids mix (TAGRO) with dolomite, and soil at the Seattle site was amended with Cedar-Grove compost (CGC) plus dolomite. TAGRO amendment diluted soil Pb by 10 to 23% and As by 12 to 25% at the Tacoma site, and CGC + dolomite resulted in 20 to 50% dilution in soil Pb at the Seattle site. Both amendments reduced Pb concentrations in vegetables by 50 to 71%, and As reductions ranged from 46 to 80%. At the Tacoma site, Pb concentrations (dry weight basis) in carrots, lettuce, and tomatoes ranged from 8.89 to 25.0, from 0.37 to 3.83, and from 0.54 to 1.24 mg kg, respectively. Plant As concentrations were below 703 μg kg (dry weight) for the vegetables and followed the order lettuce > carrot > tomato. Food-chain transfer of Pb and As in vegetables grown in contaminated urban soils were reduced by laboratory cleaning.

High-iron biosolids compost-induced changes in lead and arsenic speciation and bioaccessibility in co-contaminated soils.

The safety of urban farming has been questioned due to the potential for contamination in urban soils. A laboratory incubation, a field trial, and a second laboratory incubation were conducted to test the ability of high-Fe biosolids-based composts to reduce the bioaccessibility of soil Pb and As in situ. Lead and As bioaccessibility were evaluated using an in vitro assay. Changes in Pb, As, and Fe speciation were determined on select samples after the second laboratory incubation using μ-X-ray fluorescence mapping followed by μ-X-ray absorption near-edge structure (XANES). A compost with Fe added to wastewater treatment residuals (Fe WTR compost) added to soils at 100 g kg decreased Pb bioaccessibility in both laboratory incubations. Mixed results were observed for As. Composts tested in the field trial (Fe added as Fe powder or FeCl) did not reduce bioaccessible Pb, and limited reductions were observed in bioaccessible As. These composts had no effect on Pb bioaccessibility during the second laboratory incubation. Bulk XANES showed association of Pb with sulfates and carbonates in the control soil. μ-XANES for three points in the Fe WTR amended soil showed Pb present as Fe-sorbed Pb (88 and 100% of two points) and pyromorphite (12 and 53% of two points). Bulk XANES of the Fe WTR compost showed 97% of total Fe present as Fe. The results of this study indicate that addition of high-Fe biosolids compost is an effective means to reduce Pb accessibility only for certain types of Fe-rich materials.

Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil

Zinc oxide (ZnO) nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk) particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP) and urea) using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ–XRF) mapping and absorption fine structure spectroscopy (μ–XAFS). Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO4)2.2H2O) and zinc ammonium phosphate (Zn(NH4)PO4) species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO) at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength) of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH)2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers) was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be the same as bulk sources of ZnO.