Gary M. Pierzynski

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.

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.

The chemistry and mineralogy of phosphorus in excessively fertilized soils

Abstract Despite recent research and media attention on the environmental problems caused by nitrates, organics, and heavy metals, phosphorus (P) remains a significant pollutant of surface waters through its role in accelerated eutrophication processes. Excessively fertilized soils represent a major contributor to P loadings of surface waters. Several areas of research address the overall question of P bioavailability. The identification and characterization of P solid phases have been advanced by the application of electron optical techniques and 31P nuclear magnetic resonance (NMR) spectroscopy. Several new methods have been proposed for describing P sorption and desorption and each works well on a limited number of soils or under limited conditions. Phosphorus desorption is particularly important with respect to P bioavailability, and a generally accepted method to predict desorption does not currently exist. Some of the accumulated P in excessively fertilized soils is in organic forms. The use of 31P ...

Past, present, and future approaches for testing metals for environmental concerns and regulatory approaches

Abstract Procedural approaches used for sample preparation have remained relatively unchanged in recent years except for a trend toward extracting or digesting larger numbers of samples and the possible use of microwave digestion. The use of sequential extraction schemes for metals and metalloids has increased as a result of a growing interest in in suti remediation of contaminated soils. Here questions focus on how soil amendments or treatments have rendered metals or metalloids less reactive or bioavallable. The use of computers for control of instruments, sample presentation, and interference correction represent significant advancements for many of the routine analytical instruments in use today. The development of inductively coupled plasma‐mass spectrometry (ICP‐MS) allows for much lower detection limits for certain elements and the possibility of performing isotope ratio analysis. Synchrotron radiation‐based techniques have become more common in recent years and offer nondestructive methods for exa...

Potential bioavailability of lead, arsenic, and polycyclic aromatic hydrocarbons in compost-amended urban soils.

Urban soils may contain harmful concentrations of contaminants, such as lead (Pb), arsenic (As), and polycyclic aromatic hydrocarbons (PAHs), that can transfer from soil to humans via soil ingestion and consumption of food crops grown in such soils. The objective of this research was to assess the effectiveness of adding different compost types to reduce both direct (soil-human) and indirect (soil-plant-human) exposure of Pb, As, and PAHs to humans. A field experiment was conducted in 2011 and 2012 at an urban garden site with elevated concentrations of Pb (475 mg kg), As (95 mg kg), and PAHs (23-50 mg kg). Soil amendments were composted biosolids, noncomposted biosolids, mushroom compost, leaf compost, and a nonamended control. Collard greens, tomatoes, and carrots were then grown in the amended and nonamended soils and nonamended soils that received urea in 2011. At the beginning of the second season, N-P-K fertilizer was added to all plots. The potential for direct and indirect exposure was evaluated. Soil Pb bioaccessibility was 1 to 4.3%, and As bioaccessibility was 7.3 to 12.3%. Composted biosolids reduced the bioaccessibility of soil Pb by ∼17% compared with the control but temporarily increased the bioaccessibility of As by ∼ 69% compared with the control when soluble inorganic P concentration in soil was elevated by P fertilizer application in 2012. The bioaccessibility of soil Pb decreased by ∼38% in all treatments when soluble inorganic P concentration in soil was elevated by P fertilizer. Compost amendments reduced the concentrations of low molecular weight PAHs in soil. Regardless of the treatments, the concentrations of Pb, As, and PAHs measured in the vegetables were low or nondetectable, except for Pb in carrots. Consumption of vegetables grown at this site will cause insignificant transfer of Pb, As, and PAHs to humans.

The Freundlich adsorption isotherm constants and prediction of phosphorus bioavailability as affected by different phosphorus sources in two Kansas soils

Phosphorus (P) adsorption onto soil constituents influences P bioavailability from both agronomic and environmental perspectives. In this study, the P availability from different P sources along with utility of Freundlich adsorption coefficients on the predictability of various crop growth parameters were assessed. Two soils were amended with 150mgPkg(-1) each from six different P sources comprised of manures from two types of ruminants animals, three types of monogastric animals, and inorganic P fertilizer. Corn (Zea mays) was grown and harvested seven times under greenhouse conditions to remove P from the P amended treatments. The application of all P sources reduced the value of Freundlich K and increased the value of Freundlich 1/n and equilibrium P concentration (EPC0) in both soils compared to the un-amended control before cropping. The swine (Sus scrofa) manure (HM) resulted in significant smaller values of Freundlich K and larger values of 1/n in the P deficient Eram-Lebo soil compared to other P sources while, the opposite was true for the turkey (Meleagris gallopava) litter (TL) in the Ulysses soil. The corn biomass, tissue P concentration and P uptake were significantly influenced by all P sources during the first harvest and the total P uptake during seven harvests in both soils compared to the control treatment. Both Freundlich coefficients had strong relationships with the aforementioned corn parameters in the P deficient Eram-Lebo soil while, strength of the association was weak or missing in the Ulysses soil which had optimum levels of antecedent P.

Modeling runoff and sediment yields from combined in-field crop practices using the Soil and Water Assessment Tool

Cropland best management practice recommendations often combine improvements to both tillage and fertilizer application practices to reduce sediment losses with surface runoff. This study evaluated the impact of conventional-till and no-till management practices with surface or deep-banded fertilizer application in sorghum-soybean rotation on runoff and sediment-yield predictions using the Soil and Water Assessment Tool (SWAT) model. The model was calibrated using USDA Natural Resources Conservation Service runoff curve number for antecedent moisture condition II (CNII), saturated hydraulic conductivity, and available water capacity parameters for runoff and USLE cropping factor (Cmin) for sediment-yield predictions for three field plots (0.39 to 1.46 ha [0.96 to 3.6 ac]) with different combinations of practices and validated for three field plots (0.40 to 0.56 ha [1.0 to 1.4 ac]) over a period of 2000 to 2004. Surface runoff calibration required CNII values greater than the recommended baseline values. No-till treatments required slightly greater curve number values than the till treatment, and this difference was similar to that associated with increasing the soil hydrologic group by one classification. Generally the model underpredicted the sediment yield for all management practices. Baseline Cmin values were adequate for treatments with soil disturbance, either by tillage or fertilizer deep-banding, but best-fit Cmin values for field conditions without soil disturbance (no-till with surface-broadcast fertilizer) were 2.5 to 3 times greater than baseline values. These results indicate current model limitations in modeling undisturbed (no-till) field management conditions, and caution that models calibrated for fields or watersheds predominated by tilled soil conditions may not function equally well in testing management scenarios without tillage.

Assessment of zinc phytoavailability by diffusive gradients in thin films

Assessment of Zn phytoavailability can be predicted with routine soil extractants, but these methods generally do not perform well across a wide range of soils. The newly developed technique of diffuse gradients in thin films (DGT) has been employed to determine phytoavailable Cu concentrations, but its suitability for determining plant available Zn concentrations has not been evaluated. A greenhouse study was conducted to assess the phytotoxicity thresholds and the phytoavailability of Zn to sorghum-sudan (Sorghum vulgare var. sudanese) grass by DGT, compared with CaCl2 extraction. A range of phytoavailable Zn concentrations was created by amending sand with ZnSO4 or with two different Zn mine wastes. Plant nutrients were added as Hoagland solution. In general, increasing Zn concentrations in the sand mixtures increased Zn adsorption by DGT and decreased the sorghum-sudan yield. A critical value for 90% of the control yield was chosen as an indicator of Zn toxicity. Critical values of DGT Zn, CaCl2-extractable Zn, and plant tissue Zn were similar statistically across the three Zn sources. The performances of DGT and CaCl2 extraction for assessing Zn phytoavailability were similar. Shoot and root Zn concentrations of sorghum-sudan grass exceeded 500 mg kg(-1) for many treatments. Calcium-to-Zn ratios for shoots were <32, suggesting Zn phytotoxicity. The data suggested that Zn phytotoxicity can be induced with mine wastes, although further evaluation is needed to establish a link between mine waste and Zn phytotoxicity.

Zinc Speciation in Proximity to Phosphate Application Points in a Lead/Zinc Smelter–Contaminated Soil

The use of P to immobilize Pb in contaminated soils has been well documented. However, the influence of P on Zn speciation in soils has not been extensively examined, and these two metals often occur as co-contaminants. We hypothesized that additions of P to a Pb/Zn-contaminated soil would induce Zn phosphate mineral formation and fluid P sources would be more effective than granular P amendments. A combination of different synchrotron-based techniques, namely, spatially resolved micro-X-ray fluorescence (μ-XRF), micro-extended X-ray absorption fine structure spectroscopy (μ-EXAFS), and micro-X-ray diffraction (μ-XRD), were used to speciate Zn at two incubation times in the proximity of application points (0 to 4 mm) for fluid and granular P amendments in a Pb/Zn smelter-contaminated soil. Phosphate rock (PR), triple super phosphate (TSP), monoammonium phosphate (MAP), and fluid ammonium polyphosphate induced Zn phosphate formation. Ammonium polyphosphate was more effective at greater distances (up to 3.7 mm) from the point of P application. Phosphoric acid increased the presence of soluble Zn species because of increased acidity. Soluble Zn has implications with respect to Zn bioavailability, which may negatively impact vegetation and other sensitive organisms. Although additions of P immobilize Pb, this practice needs close monitoring due to potential increases in Zn solubility in a Pb/Zn smelter-contaminated soil.