Sorption of trace metals by standard and micro suction cups in the absence and presence of dissolved organic carbon

Both the bioavailability of a trace metal (TM) in a soil and the risk of leaching to the ground water are linked to the metals concentration in the soil solution. Sampling soil solution by tension lysimetry with suction cups is a simple and established technique that is increasingly used for monitoring dissolved TM in soils. Of major concern, however, is the sorption of TM by the walls of the samplers. Metal sorption by different materials used in suction cups can vary widely, depending also on the chemistry of the soil solution. We compared the sorption of Cu, Zn, Cd, and Pb by different standard-size and micro suction cups in the laboratory at two pH values (4.5 and 7.5 or 8.0) in absence and presence of dissolved organic carbon (DOC). In addition, we investigated the sorption of DOC from different origins by the cup materials. At both pH values, the weakest sorption of all four TMs was exhibited by standard-size suction cups based on nylon membranes and by hollow fibers made from polyvinyl alcohol (PVA). At alkaline pH, borosilicate glass, ceramic materials, and polytetrafluorethylene (PTFE) mixed with silicate were characterized by generally strong sorption of all investigated TMs. In addition, Cu and Pb were strongly sorbed at low pH by PTFE-silicate and a ceramic material used for the construction of standard-size suction cups. On the other hand, sorption of Cu, Zn, and Cd by ceramic capillaries produced from pure aluminum oxide was negligible at low pH. Micro suction cups made of an unknown polymerous tube sorbed Cu strongly, but were well suited to monitor Zn, Cd, and Pb at low pH, and, in the presence of DOC, also at high pH. Major cations (Na+, Mg2+, K+, Ca2+) and anions (Cl-, NO3-, SO4(2-)) were not or very weakly sorbed by all cup materials, except for Mg2+, K+, and Ca2+ by borosilicate glass at pH 7.5. Trace metal sorption by suction cups was generally greatly reduced in the presence of DOC, especially at alkaline pH. The sorption of DOC itself depended on its source. Dissolved organic carbon from leaf litter extracts with a probably large hydrophobic fraction was sorbed more strongly than mainly hydrophilic DOC from a mineral soil solution.     

Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Use of diammonium phosphate to reduce heavy metal solubility and transport in smelter-contaminated soil

Phosphate treatments can reduce metal dissolution and transport from contaminated soils. However, diammonium phosphate (DAP) has not been extensively tested as a chemical immobilization treatment. This study was conducted to evaluate DAP as a chemical immobilization treatment and to investigate potential solids controlling metal solubility in DAP-amended soils. Soil contaminated with Cd, Pb, Zn, and As was collected from a former smelter site. The DAP treatments of 460, 920, and 2300 mg P kg-1 and an untreated check were evaluated using solute transport experiments. Increasing DAP decreased total metal transported. Application of 2300 mg P kg-1 was the most effective for immobilizing Cd, Pb, and Zn eluted from the contaminated soil. Metal elution curves fitted with a transport model showed that DAP treatment increased retardation (R) 2-fold for Cd, 6-fold for Zn, and 3.5-fold for Pb. Distribution coefficients (Kd) increased with P application from 4.0 to 9.0 L kg-1 for Cd, from 2.9 to 10.8 L kg-1 for Pb, and from 2.5 to 17.1 L kg-1 for Zn. Increased Kd values with additional DAP treatment indicated reduced partitioning of sorbed and/or precipitated metal released to mobile metal phases and a concomitant decrease in the concentration of mobile heavy metal species. Activity-ratio diagrams indicated that DAP decreased solution Cd, Pb, and Zn by forming metal-phosphate precipitates with low solubility products. These results suggest that DAP may have potential for protecting water resources from heavy metal contamination near smelting and mining sites.     

Food safety assessment of planting patterns of four vegetable-type crops grown in soil contaminated by electronic waste activities

A field experiment was conducted to assess the effect of crop and planting pattern on levels of cadmium (Cd), lead (Pb), and copper (Cu) in crops grown in soil contaminated by electronic waste. The crops were maize (Zea mays L. var. Shentian-1), tomato (Solanum lycopersicum L. var. Zhongshu-4), cabbage (Brassica oleracea L. var. Jingfeng-1), and pakchoi (Brassica chinensis (L.) Makino. var. Youdonger-Hangzhou). The planting patterns were crop monoculture, crop co-planted with a legume, and crop co-planted with another crop. Metal concentrations in the edible parts of the crops varied with types of metals and crops. Pb concentration was higher in leafy vegetables (cabbage and pakchoi) than in maize or tomato, Cd concentration was higher in tomato and pakchoi than in maize or cabbage, and Cu concentration was higher in maize and pakchoi than in tomato or cabbage. Metal concentrations in the edible part were also influenced by planting pattern. Relative to monoculture, co-planting and especially co-planting with Japanese clover tended to decrease Pb accumulation and increase Cd accumulation. According to the maximum permissible concentration (MPC) standard of the National Standard Agency in China, only maize (under all planting patterns) could be safely consumed. Because co-planting tended to increase Cd accumulation even in maize, however, the results suggest that maize monoculture is the optimal crop and planting pattern for this kind of contaminated soil.     

Perfluorinated phosphine oxide and sulfides as extractants for heavy metals and radionuclides

New highly fluorinated monodentate and bidentate phosphine oxide compounds of the type {CF(3)(CF(2))(n)CH(2)CH(2)}(3)PO (n = 5, 9) and [{CF(3)(CF(2))(5)CH(2)CH(2)}(2)P(O)CH(2)CH(2)P(O){CH(2)CH(2)(CF(2))(5)CF(3)}] have been prepared. Their ability to extract a number of metals and radionuclides from aqueous solutions into perfluorinated solvents has been established and the extractable species investigated. All extractants extract the metals As(V), Cd(II), Co(II), Cr(VI), Hg(II), Pb(II), and Sn(II) with >75% removal. In addition, the radioisotopes (90)Sr(II), (133)Ba(II), and U(VI) have been investigated, whilst (59)Fe(III) has been used to model the extraction of plutonium. (133)Ba(II) shows a high distribution ratio for monodentate phosphine oxides, whilst for UO(2)(2+) and (59)Fe(III) bidentate phosphine oxides are superior.     

Sorption and desorption of cadmium by different fractions of biosolids-amended soils

To evaluate the importance of both the inorganic and organic fractions in biosolids on Cd chemistry, a series of Cd sorption and desorption batch experiments (at pH 5.5) were conducted on different fractions of soils from a long-term field experimental site. The slope of the Cd sorption isotherm increased with rate of biosolids and was different for the different biosolids. Removal of organic carbon (OC) reduced the slope of the Cd sorption isotherm but did not account for the observed differences between biosolids-amended soils and a control soil, indicating that the increased adsorption associated with biosolids application was not limited to the increased OC from the addition of biosolids. Removal of both OC and Fe/Mn further reduced the slopes of Cd sorption isotherms and the sorption isotherm of the biosolids-amended soil was the same as that of the control, indicating both OC and Fe/Mn fractions added by the biosolids were important to the increased sorption observed for the biosolids-amended soil samples. Desorption experiments failed to remove from 60 to 90% of the sorbed Cd. This "apparent hysteresis" was higher for biosolids-amended soil than the control soil. Removal of both OC and Fe/Mn fractions was more effective in removing the observed differences between the biosolids-amended soil and the control than either alone. Results show that Cd added to biosolids-amended soil behaves differently than Cd added to soils without biosolids and support the hypothesis that the addition of Fe and Mn in the biosolids increased the retention of Cd in biosolids-amended soils.     

Enhanced transformation of lead speciation in rhizosphere soils using phosphorus amendments and phytostabilization: an x-ray absorption fine structure spectroscopy investigation

To formulate successful phytostabilization strategies in a shooting range soil, understanding how heavy metals are immobilized at the molecular level in the rhizosphere soil is critical. Lead (Pb) speciation and solubility in rhizosphere soils of five different plant species were investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical extraction. The EXAFS analysis indicated that Pb occurred as PbCO (37%), Pb sorbed to organic matter (Pb-org: 15%), and Pb sorbed to pedogenic birnessite and/or ferrihydrite (Pb-ox: 36%) in the bulk soil. Comparison of the EXAFS spectra between bulk and rhizosphere soils demonstrated notable differences in fine structure, indicating that Pb species had been modified by rhizosphere processes. The estimated proportion of PbCO (25%) in the buckwheat soil was smaller than the other rhizosphere soils (35-39%). The addition of P significantly reduced Pb solubility in the bulk and rhizosphere soil except in the rhizosphere of buckwheat, for which the Pb solubility was 10-fold greater than in the other P-amended soils. This larger solubility in the buckwheat rhizosphere could not be explained by the total Pb speciation in the soil but was presumably related to the acidifying effect of buckwheat, resulting in a decrease of the soil pH by 0.4 units. The reduced Pb solubility by P amendment resulted from the transformation of preexisting PbCO (37%) into Pb(PO)Cl (26-32%) in the bulk and rhizosphere soils. In the P-amended rhizosphere soils, Pb-org species were no longer detected, and the Pb-ox pool increased (51-57%). The present study demonstrated that rhizosphere processes modify Pb solubility and speciation in P-amended soils and that some plant species, like buckwheat, may impair the efficiency of Pb immobilization by P amendments.     

In situ stabilization of soil lead using phosphorus and manganese oxide: influence of plant growth

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.     

Chemical immobilization of lead, zinc, and cadmium in smelter-contaminated soils using biosolids and rock phosphate

Chemical immobilization, an in situ remediation method where inexpensive chemicals are used to reduce contaminant solubility in contaminated soil, has gained attention. We investigated the effectiveness of lime-stabilized biosolid (LSB), N-Viro Soil (NV), rock phosphate (RP), and anaerobic biosolid (AB) to reduce extractability and plant and gastrointestinal (GI) bioavailability in three Cd-, Pb-, and Zn-contaminated soils from smelter sites. Treated (100 g kg(-1) soil) and control soils were incubated at 27 degrees C and -0.033 MPa (0.33 bar) water content for 90 d. The effect of soil treatment on metal extractability was evaluated by sequential extraction, on phytoavailability by a lettuce bioassay (Lactuca sativa L.), on human GI availability of Pb from soil ingestion by the Physiologically Based Extraction Test. The largest reductions in metal extractability and phytoavailability were from alkaline organic treatments (LSB and NV). Phytotoxic Zn [1188 mg Zn kg(-1) extracted with 0.5 M Ca(NO3)2] in Blackwell soil (disturbed soil) was reduced by LSB, NV, and RP to 166, 25, and 784 mg Zn kg(-1), respectively. Rock phosphate was the only treatment that reduced GI-available Pb in both gastric and intestinal solutions, 23 and 92%, respectively. Alkaline organic treatments (LSB, NV) decreases Cd transmission through the food chain pathway, whereas rock phosphate decreases risk from exposure to Pb via the soil ingestion pathway. Alkaline organic treatments can reduce human exposure to Cd and Pb by reducing Zn phytotoxicity and revegetation of contaminated sites.     

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.     

Analysis of transgenic Indian mustard plants for phytoremediation of metal-contaminated mine tailings

Transgenic Indian mustard [Brassica juncea (L.) Czern.] plants overproducing the enzymes gamma-glutamylcysteine synthetase (ECS) or glutathione synthetase (GS) were shown previously to have increased levels of the metal-binding thiol peptides phytochelatins and glutathione, and enhanced Cd tolerance and accumulation. Furthermore, transgenic Indian mustard plants overexpressing adenosine triphosphate sulfurylase (APS) were shown to have higher levels of glutathione and total thiols. These results were obtained with a solution culture. To better examine the phytoremediation potential of these transgenics, a greenhouse experiment was performed in which the transgenics were grown on metal-contaminated soil collected from a USEPA Superfund site near Leadville, Colorado. A grass mixture used for revegetation of the site was included for comparison. The ECS and GS transgenics accumulated significantly (P < 0.05) more metal in their shoot than wild-type (WT) Indian mustard, while the APS plants did not. Of the six metals tested, the ECS and GS transgenics accumulated 1.5-fold more Cd, and 1.5- to 2-fold more Zn, compared with wild-type Indian mustard. Furthermore, the ECS transgenics accumulated 2.4- to 3-fold more Cr, Cu, and Pb, relative to WT. The grass mixture accumulated significantly less metal than Indian mustard: approximately 2-fold less Cd, Cu, Mn, and Zn, and 5.7-fold less Pb than WT Indian mustard. All transgenics removed significantly more metal from the soil compared with WT Indian mustard or an unplanted control. While WT did not remove more metal than the unplanted control for any of the metals tested, all three types of transgenics significantly reduced the soil metal concentration, and removed between 6% (Zn) and 25% (Cd) of the soil metal. This study is the first to demonstrate enhanced phytoextraction potential of transgenic plants using polluted environmental soil. The results confirm the importance of metal-binding peptides for plant metal accumulation and show that results from hydroponic systems have value as an indicator for phytoremediation potential.     

Contamination time effect on lead and cadmium fractionation in a tropical coastal clay

The capability of a tropical coastal clay to immobilize lead (Pb) and cadmium (Cd) was investigated in laboratory batch sorption tests conducted under acidic, neutral, and slightly alkaline conditions. The contact time was extended to 65 d. The distribution of Pb and Cd among various sorbed phases was examined using a sequential extraction technique. The sorbed phases were fractionated into the exchangeable, carbonate, reducible, organic, and residual fractions. There were only small changes in the total Pb and Cd sorption beyond a 1-d sorption period. The metal fractionation results show that the amount of Pb and Cd in various fractions changed with sorption time, and the changes were pH-dependent. These changes could be attributed to mineral dissolution and transformation or redistribution of the sorbed phases. Transformation of the sorbed phases resulted in increasing Pb and Cd retention in the more persistent fractions with time, at the expense of reductions in the loosely bound fractions. Nevertheless, Pb and Cd fractionation in the solid phase appeared to reach equilibrium within the 65-d sorption period. These Pb and Cd fractionation results reflect the effect of contamination time on the heavy metal lability and bioavailability in the subsurface environment.     

Effect of biosolids processing on lead bioavailability in an urban soil

The potential for biosolids products to reduce Pb availability in soil was tested on a high Pb urban soil with biosolids from a treatment plant that used different processing technologies. High Fe biosolids compost and high Fe + lime biosolids compost from other treatment plants were also tested. Amendments were added to a Pb-contaminated soil (2000 mg kg(-1) Pb) at 100 g kg(-1) soil and incubated for 30 d. Reductions in Pb bioavailability were evaluated with both in vivo and in vitro procedures. The in vivo study entailed feeding a mixture of the Pb-contaminated soil and AIN93G Basal Mix to weanling rats. Three variations of an in vitro procedure were performed as well as conventional soil extracts [diethylenetriaminepentaacetic acid (DTPA) and Ca(NO3)2] and sequential extraction. Addition of the high Fe compost reduced the bioavailability of soil Pb (in both in vivo and in vitro studies) by 37 and 43%, respectively. Three of the four compost materials tested reduced Pb bioavailability more than 20%. The rapid in vitro (pH 2.3) data had the best correlation with the in vivo bone results (R = 0.9). In the sequential extract, changes in partitioning of Pb to Fe and Mn oxide fractions appeared to reflect the changes in in vivo Pb bioavailability. Conventional extracts showed no changes in metal availability. These results indicate that addition of 100 g kg(-1) of high Fe and Mn biosolids composts effectively reduced Pb availability in a high Pb urban soil.     

In situ soil treatments to reduce the phyto- and bioavailability of lead, zinc, and cadmium

A study was established near a former Zn and Pb smelter to test the ability of soil amendments to reduce the availability of Pb, Zn, and Cd in situ. Soil collected from the field was amended in the lab with P added as 1% P-H3PO4, biosolids compost added at 10% (referred to hereafter as "compost"), and a high-Fe by-product (referred to hereafter as "Fe") + P-triple superphosphate (TSP) (2.5% Fe + 1% P-TSP) and incubated under laboratory conditions at a constant soil pH. Changes in Pb bioavailability were measured with an in vitro test and a feeding study with weanling rats. Field-amended and incubated soils using these plus additional treatments were evaluated using the in vitro extraction and tall fescue (Festuca arundinacea Schreb. cv. Kentucky-31) metal concentration. Reductions were observed across all parameters but were not consistent. In the feeding study, the 1% P-H3PO4 and compost treatments resulted in a decrease of 26% in rat tissue Pb concentration compared with the control soil. The 2.5% Fe + 1% P-TSP showed a 39% decrease. The 1% P-H3PO4 treatment caused the greatest reduction in in vitro extractable Pb from field samples (pH 2.2) with a measured reduction of 66%, while the compost treatment had a 39% reduction and the 2.5% Fe + 1% P-TSP treatment a 50% reduction. The in vitro extraction (pH 1.5) run on field samples showed no reduction in the compost or Fe treatments. The 1% P-H3PO4 treatment was the most effective at reducing plant Pb, Zn, and Cd.     

Ethylenediaminedissuccinate as a new chelate for environmentally safe enhanced lead phytoextraction

Using a soil column experiment, we compared the effect of a single dose and weekly additions of ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedissuccinate (EDDS) on the uptake of Pb, Zn, and Cd by Chinese cabbage [Brassica rapa L. subsp. pekinensis (Lour.) Hanelt], and on the leaching of heavy metals through the soil profile. The analysis of plant material revealed that both chelates increased the concentrations of Pb and, to a lesser extent, also of Zn and Cd in the leaves of the test plant. The most effective applications were single doses of 10 mmol EDTA and EDDS kg(-1) soil, which caused the concentrations of Pb in the shoots to increase 94.2- and 102.3-fold, respectively, relative to the control. The same dose of EDTA increased the concentration of Zn and Cd in the leaves 4.3- and 3.8-fold and of EDDS 4.7- and 3.5-fold, respectively. In treatments with weekly additions and lower concentrations of both chelates, EDTA was more effective than EDDS in increasing the plant uptake of Pb. In soil columns treated with weekly additions of 10 mmol kg(-1) EDTA, on average 22.7, 7.0, and 39.8% of initial total Pb, Zn, and Cd in the soil were leached through the soil profile. The same amount of EDDS caused much lower leaching of Pb and Cd--only 0.8 and 1.5% of initial total concentrations. Leaching of Zn, 6.2% of the total concentration, was comparable with the EDTA treatment. A biotest with red clover (Trifolium pratense L.) indicated a greater phytotoxic effect of EDTA than EDDS addition. EDDS was also less toxic to soil fungi, as determined by phospholipid fatty acid (PLFA) analysis, and caused less stress to soil microorganisms, as indicated by the trans to cis PLFA ratio. Chelate addition did not prevent the development of arbuscular mycorrhiza on red clover.     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.     

Revegetation of high zinc and lead tailings with municipal biosolids and lime: greenhouse study

Acidic (pH 4.1) and high Cd, Pb, and Zn mine tailings (mean +/- SD: 17 +/- 0.4, 3800 +/- 100, and 3500 +/- 100 mg kg(-1), respectively) from an alluvial tailings deposit in Leadville, Colorado were amended with municipal biosolids (BS) (224 Mg ha(-1)) and different types of lime (calcium carbonate equivalent of 224 Mg ha(-1) CaCO3) in a greenhouse column study to test the ability of the amendments to neutralize surface and subsoil acidity and restore plant growth. The types of lime included coarse, agricultural, and fine-textured lime (CL, AL, and FL), sugar beet lime (SBL), and lime kiln dust (LK). The FL was also added alone. All treatments increased bulk pH in the amended horizon in comparison to the control, with the most significant increases observed in the FL, SBL+BS, and LK+BS treatments (7.33, 7.34, and 7.63, respectively). All treatments, excluding the FL, increased the pH in the horizon directly below the amended layer, with the most significant increases observed in the SBL+BS and LK+BS treatments (6.01 and 5.41, respectively). Significant decreases in 0.01 M Ca(NO3)2-extractable Zn and Cd were observed in the subsoil for all treatments that included BS, with the largest decrease in the SBL+BS treatment (344 and 3.9 versus 4 and 0.1 mg kg(-1) Zn and Cd, respectively). Plant growth of annual rye (Lolium multiflorum L.) was vigorous in all treatments that included BS with plant Zn, Cd, and Pb concentrations reduced over the control.     

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4, was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.     

Ecosystem function in alluvial tailings after biosolids and lime addition

Municipal biosolids and agricultural limestone were incorporated into the surface of alluvial highly acidic, metal-contaminated mine tailings in Leadville, CO, in 1998. Amended sites were seeded and a plant cover was subsequently established. A range of chemical and biological parameters were measured over time to determine if treatment was sufficient to restore ecosystem function. An uncontaminated upstream control (UUC), a contaminated vegetated area (CVA), and soils collected from the tailings deposits before amendment addition were used for comparison. Standard soil extracts showed decreases in extractable Pb, Zn, and Cd in the amended soils. Increased CO2 evolution, reduced N2O, and elevated NO3- in the amended tailings indicated an active microbial community. Levels of CO2 and NO3- were elevated in comparison with the CVA and UUC. Ryegrass (Lolium perenne L.) and earthworm (Eisenia foetida) survival and metal uptake values were similar in amended tailings to a laboratory control soil. Ryegrass and worms in unamended tailings died. Field plant diversity was lower in amended areas than in CVA or UUC, with a higher percentage of the vegetative cover consisting of grasses. Small mammal analysis showed a low potential for elevated body Cd and Pb in the amended tailings. A re-entrainment study using fathead minnows (Pimephales promelas) showed no danger for resuspended amended tailings, as survival of fish was similar to the laboratory control. Data suggest that ecosystem function has been restored to the amended tailings, but that these systems are not yet in equilibrium.