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.     

Adsorption of cadmium on biosolids-amended soils

Debate exists over the biosolid phase (organic or inorganic) responsible for the reduction in phytoavailable Cd in soils amended with biosolids as compared with soils amended with inorganic salts. To test the importance of these two phases, adsorption isotherms were developed for soil samples (nine biosolids-amended soils and their five companion controls) and two biosolids samples from five experimental sites with documented histories of biosolids application. Subsamples were treated with 0.7 M NaClO to remove organic carbon. Cadmium nitrate was added to both moist soil samples and their soil inorganic fractions (SIF) in a 0.01 M Ca(NO3)2 solution at three pH levels (6.5, 5.5, and 4.5), and equilibrated at 22 +/- 1 degrees C for at least 48 h. Isotherms of Cd adsorption for biosolids-amended soil were intermediate to the control soil and biosolids. Decreasing pH did not remove the difference between these isotherms, although adsorption of Cd decreased with decreasing pH level. Organic matter removal reduced Cd adsorption on all soils but had little influence on the observed difference between biosolids-amended and control soils. Thus, increased adsorption associated with biosolids application was not limited to the organic matter addition from biosolids; rather, the biosolids application also altered the adsorptive properties of the SIF. The greater affinity of the inorganic fraction of biosolids-amended soils to adsorb Cd suggests that the increased retention of Cd on biosolids-amended soils is independent of the added organic matter and of a persistent nature.     

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.     

Effects of elevated carbon dioxide on soils in a Florida scrub oak ecosystem

The results of a 3-yr study on the effects of elevated CO2 on soil N and P, soil pCO2, and calculated CO2 efflux in a fire-regenerated Florida scrub oak ecosystem are summarized. We hypothesized that elevated CO2 would cause (i) increases in soil pCO2 and soil respiration and (ii) reduced levels of soil-available N and P. The effects of elevated CO2 on soil N availability differed according to the method used. Results of resin lysimeter collections and anion exchange membrane tests in the field showed reduced NO3- in soils in Years 1 and 3. On the other hand, re-analysis of homogenized, buried soil bags after 1 yr suggested a relative increase in N availability (lower C to N ratio) under elevated CO2. In the case of P, the buried bags and membranes suggested a negative effect of CO2 on P during the first year; this faded over time, however, as P availability declined overall, probably in response to P uptake. Elevated CO2 had no effect on soil pCO2 or calculated soil respiration at any time, further suggesting that plant rather than microbial uptake was the primary factor responsible for the observed changes in N and P availability with elevated CO2.     

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.     

Heavy metal distribution and chemical speciation in tailings and soils around a Pb-Zn mine in Spain

Soil pollution by lead, zinc, cadmium and copper was characterized in the mine tailings and surrounding soils (arable and pasture lands) of an old Spanish Pb-Zn mine. Sixty soil samples were analyzed, determining the total metal concentration by acid digestion and the chemical fractionation of Pb and Zn by the modified BCR sequential extraction method. Samples belonging to mine waste areas showed the highest values, with mean concentrations of 28,453.50 mg kg(-1) for Pb, 7000.44 mg kg(-1) for Zn, 20.57 mg kg(-1) for Cd and 308.48 mg kg(-1) for Cu. High concentrations of Pb, Zn and Cd were found in many of the samples taken from surrounding arable and pasture lands, indicating a certain extent of spreading of heavy metal pollution. Acidic drainage and wind transport of dust were proposed as the main effects causing the dispersion of pollution. Sequential extraction showed that most of the Pb was associated with non-residual fractions, mainly in reducible form, in all the collected samples. Zn appeared mainly associated with the acid-extractable form in mine tailing samples, while the residual form was the predominant one in samples belonging to surrounding areas. Comparison of our results with several criteria reported in the literature for risk assessment in soils polluted by heavy metals showed the need to treat the mine tailings dumped in the mine area.     

Response of soil microbiological activities to cadmium,lead, and zinc salt amendments

Heavy metal pollution of soil has been recognized as a major factor impeding soil microbial processes. From this perspective, we studied responses of the soil biological activities to metal stress simulated by soil amendment with Zn, Pb, and Cd chlorides. The amounts of heavy metal salts added to five metal-polluted soils and four nonpolluted soils were selected to match the total metal concentrations typically found in polluted soils of the Silesia region of Poland. From the perspective of soil quality, metal mobility in amended soils could not be described by simple functions of pH or organic matter. Reaction of Pb with the soil caused strong immobilization with less than 1% of the Pb amendment recovered by 0.01 M CaCl2 extractions. Immobilization of Cd was also significant, whereas immobilization of the Zn amendment was much weaker than that of Cd or Pb. The Zn amendment had substantial inhibitory effect on soil dehydrogenase, acid and alkaline phosphatase, arylsulfatase, urease, and nitrification potential. Generally, Cd and Pb had limited or stimulatory effect on most of these biological activities, with an exception of Pb strongly inhibiting soil urease. The effect of the metal amendments on biological activities could not be satisfactorily accounted for by metal toxicity because no strong relationship was observed between extractable metal content and the degree of inhibition. The Zn amendment had a significant effect on soil pH, resulting in confounding effects of pH and Zn toxicity on activities. Metal amendment experiments seem to be of limited utility for meaningful assessment of metal contamination effects on soil quality.     

Extent of pyrolysis impacts on fast pyrolysis biochar properties

A potential concern about the use of fast pyrolysis rather than slow pyrolysis biochars as soil amendments is that they may contain high levels of bioavailable C due to short particle residence times in the reactors, which could reduce the stability of biochar C and cause nutrient immobilization in soils. To investigate this concern, three corn ( L.) stover fast pyrolysis biochars prepared using different reactor conditions were chemically and physically characterized to determine their extent of pyrolysis. These biochars were also incubated in soil to assess their impact on soil CO emissions, nutrient availability, microorganism population growth, and water retention capacity. Elemental analysis and quantitative solid-state C nuclear magnetic resonance spectroscopy showed variation in O functional groups (associated primarily with carbohydrates) and aromatic C, which could be used to define extent of pyrolysis. A 24-wk incubation performed using a sandy soil amended with 0.5 wt% of corn stover biochar showed a small but significant decrease in soil CO emissions and a decrease in the bacteria:fungi ratios with extent of pyrolysis. Relative to the control soil, biochar-amended soils had small increases in CO emissions and extractable nutrients, but similar microorganism populations, extractable NO levels, and water retention capacities. Corn stover amendments, by contrast, significantly increased soil CO emissions and microbial populations, and reduced extractable NO. These results indicate that C in fast pyrolysis biochar is stable in soil environments and will not appreciably contribute to nutrient immobilization.     

Application of two organic wastes in a soil polluted by lead: effects on the soil enzymatic activities

The effects of adding a crushed cotton gin compost (CCGC) and a poultry manure (PM) on the enzymatic activities of a Typic Xerofluvent soil polluted with Pb were studied in the laboratory. Three hundred grams of sieved soil (<2 mm) were mixed with PM at a rate of 10% or CCGC at a rate of 17.2%, applying to the soil the same amount of organic matter with each organic amendment. Urease, protease-BBA, beta-glucosidase, alkaline phosphatase, and arylsulfatase activities were measured at four different incubation times (1, 7, 15, and 45 d) in soils containing seven concentrations (100, 250, 500, 1000, 2500, 5000, and 8000 mg kg-1) of Pb, and in the same soils amended with CCGC and PM. In all treatments and incubation times, the inhibition percentage of soil enzyme activities by Pb was lower in soils amended with the PM and CCGC than in nonamended soils, and it differed with the organic amendment. In this respect, the in the 8000 mg Pb kg-1 treatment at the end of the incubation period, the protease-BBA activity inhibition percentage was lower (14.7 and 33.9% lower, respectively) in CCGC- than in PM-amended soils. Since the adsorption capacity of Pb was higher in CCGC- than the PM-amended soils, the addition of organic wastes with higher humic acid concentration is more beneficial for remediation of soils polluted with Pb.     

Germination,Growth, and Nodulation of Sesbania rostrata Grown in Pb/Zn Mine Tailings

Sesbania rostrata in pure and amended Pb/Zn tailings. About 90% of seeds of S. rostrata germinated in pure Pb/Zn tailings, which contained high concentrations of Pb, Zn, Cu, and Cd. Although seedling growth suffered from the adverse environment of Pb/Zn tailings, they became established on tailings stands, in the greenhouse, as well as on the actual tailings dam, and completed their life cycle in 4 months. Dry matter production and nitrogen accumulation was 3200 kg/ha and 69.4 kg/ha, respectively in the actual tailings dam. Applying inorganic fertilizer to Pb/Zn tailings led to no obvious improvement in growth and nodulation of S. rostrata, while tailings amended by river sediment or domestic refuse rich in organic matter improved the growth and nodulation of the species. Azorhizobium caulinodans survived and formed N-fixing stem and root nodules in S. rostrata grown in pure Pb/Zn tailings with a nodule biomass exceeding 300 mg fresh matter per plant.     

Migration of trace elements from pyrite tailings in carbonate soils

In the carbonate soils contaminated by a toxic spill from a pyrite mine (Aznalcóllar, southern Spain), a study was made of a thin layer (thickness = 4 mm) of polluted soil located between the pyrite tailings and the underlying soil. This layer, reddish-yellow in color due to a high Fe content, formed when sulfates (from the oxidation of sulfides) infiltrated the soil, causing acidification (to pH 5.6 as opposed to 8.0 of unaffected soil) and pollution (in Zn, Cu, As, Pb, Co, Cd, Sb, Bi, Tl, and In). The less mobile elements (As, Bi, In, Pb, Sb, and Tl) concentrated in the uppermost part of the reddish-yellow layer, with concentration decreasing downward. The more mobile elements (Co, Cd, Zn, and Cu) tended to precipitate where the pH was basic, toward the bottom of the layer or in the upper part of the underlying soil. The greatest accumulations occurred within the first 6 mm in overall soil depth, and were negligible below 15 mm. In addition, the acidity of the solution from the tailings degraded the minerals of the clay fraction of the soils, both the phyllosilicates as well as the carbonates. Also, within the reddish-yellow layer, gypsum formed autigenically, together with complex salts of sulfates of Fe, Al, Zn, Ca, and Mn, jarosite, and oxihydroxides of Fe.     

Weathering of lead bullets and their environmental effects at outdoor shooting ranges

Lead contamination at shooting range soils is of great environmental concern. This study focused on weathering of lead bullets and its effect on the environment at five outdoor shooting ranges in Florida, USA. Soil, plant, and water samples were collected from the ranges and analyzed for total Pb and/or toxicity characteristic leaching procedure (TCLP) Pb. Selected bullet and berm soil samples were mineralogically analyzed with X-ray diffraction and scanning electron microscopy. Hydrocerussite [Pb3(CO3)2(OH)2] was found in both the weathered crusts and berm soils in the shooting ranges with alkaline soil pH. For those shooting ranges with acidic soil pH, hydrocerussite, cerussite (PbCO3), and small amount of massicot (PbO) were predominantly present in the weathered crusts, but no lead carbonate mineral was found in the soils. However, hydroxypyromorphite [(Pb10(PO4)6(OH)2] was formed in a P-rich acidic soil, indicating that hydroxypyromorphite can be a stable mineral in P-rich shooting range soil. Total Pb and TCLP Pb in the soils from all five shooting ranges were significantly elevated with the highest total Pb concentration of 1.27 to 4.84% (w/w) in berm soils. Lead concentrations in most sampled soils exceeded the USEPA's critical level of 400 mg Pb kg(-1) soil. Lead was not detected in subsurface soils in most ranges except for one, where elevated Pb up to 522 mg kg(-1) was observed in the subsurface, possibly due to enhanced solubilization of organic Pb complexes at alkaline soil pH. Elevated total Pb concentrations in bermudagrass [Cynodon dactylon (L.) Pers.] (up to 806 mg kg(-1) in the aboveground parts) and in surface water (up to 289 microg L(-1)) were observed in some ranges. Ranges with high P content or high cation exchange capacity showed lower Pb mobility. Our research clearly demonstrates the importance of properly managing shooting ranges to minimize adverse effects of Pb on the environment.     

Dissolved organic carbon dynamics in a riparian aquifer: effects of hydrology and nitrate enrichment

The capacity of riparian soils to remove nitrate (NO3) from ground water is well established, but the effects of ground water NO3(-)-enrichment on C dynamics are not well studied. We incubated horizontal cores of aquifer material extracted from beneath moderately well-drained (MWD) and poorly drained (PD) soils in a riparian forest in Rhode Island, USA for 132 d, and dosed (flow rate, 170 mL d(-1); dissolved O2, 2 in PD and 5 mg L(-1) in MWD cores) with ground water amended with either Br-, Br(-)+ NO3- (10 mg N L(-1)), or Br(-) + NO3(-) + DOC (20 mg C L(-1)). The DOC was extracted from forest floor material and added during the first 56 d of the experiment. Addition of NO3- had limited effect on CO2 production while DOC amendment had a significant effect in the PD but not in the MWD mesocosms. Total CO2 production (mg CO2-C kg(-1) soil) was 6.3, 7.0, and 10.1 in the PD and 3.6, 4.0, and 4.5 in the MWD cores amended with Br-, Br(-) + NO3-, and Br(-) + NO3(-) + DOC, respectively. Carbon balance (C(bal) = DOC(in) - (DOC(out) + CO2-C) showed a net C retention of 8.0 mg C kg(-1) soil in the DOC-amended MWD cores (equivalent to 50% of the DOC added), and a net C loss of 8.3 mg C kg(-1) soil in similarly treated PD cores. The lack of C retention in the PD cores was ascribed to reductive dissolution of minerals implicated in DOC sorption. These findings underscore that there is marked variation in C dynamics in riparian aquifers that has the potential to influence the fate of NO3- and DOC in the landscape.     

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.     

Assessment of metal availability in smelter soil using earthworms and chemical extractions

Chemical immobilization is a relatively inexpensive in situ remediation method that reduces soil contaminant solubility, but the ability of this remediation treatment to reduce heavy metal bioavailability and ecotoxicity to soil invertebrates has not been evaluated. Our objectives were to (i) assess the ability of chemical immobilization amendments (municipal sewage sludge biosolids and rock phosphate) to reduce metal bioavailability and toxicity in a toxic metal-contaminated smelter soil and (ii) evaluate soil extraction methods using Ca(NO3)2 solution or ion-exchange membranes coated with diethylenetriaminepentaacetic acid (DTPA) as surrogate measures of metal bioavailability and ecotoxicity. We treated a soil contaminated by Zn and Pb milling and smelting operations and an uncontaminated control soil with lime-stabilized municipal biosolids (LSB), rock phosphate (RP), or anaerobically digested municipal biosolids (SS) and evaluated lethality of the remediated soils to earthworm (Eisenia fetida Savigny). Lime-stabilized municipal biosolids was the only remediation amendment to successfully immobilize lethal levels of Zn in the smelter soil (14-d cumulative mortality < or = 15%). Calcium nitrate-extractable Zn in the lethal Zn smelter soil-amendment combinations was 11.5 to 18.2 mmol/kg, compared with the nonlethal LSB amended soil (0.62 mmol/kg). The Ca(NO3)2-extractable Zn-based median lethal concentration (LC50) of 6.33 mmol/kg previously developed in Zn-spiked artificial soils was applicable in the remediated smelter soils despite a 14-fold difference in total Zn concentration. Chelating ion-exchange membrane uptake among the soils was highly variable (mean CV = 39%) compared with the Ca(NO3)2-extraction (mean CV = 1.9%) and not well related to earthworm toxicity.     

Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Cadmium and zinc in vegetation and litter of a voluntary woodland that has developed on contaminated sediment-derived soil

Vegetation that develops spontaneously on metal-contaminated soils presents an opportunity to evaluate both metal bioavailability and the risks posed to biota. The behavior of Cd and Zn in the species of a spontaneously developed woodland, colonizing a canal embankment, has been investigated. Nitric-acid-extractable metal concentrations in the sediment-derived substrate ranged between 5.0 to 376 mg kg(-1)dry wt. Cd and 83.0 to 784 mg kg(-1)dry wt. Zn. The woodland is dominated by Willow (Salix) species. Salix caprea selectively accumulated Cd in all stem tissues, in contrast to S. viminalis, which regulated tissue Cd content. Both species showed an effective regulation of tissue Zn. Cadmium uptake by S. caprea was correlated with differences in soil pH, while Zn uptake was not. There was no relationship between tissue metal concentrations and soil metal nitric acid-extractable concentrations. Other aspects of ecosystem function appeared unaffected by the elevated Cd flux in S. caprea; leaf litter organisms present represented all major groups and there was no accumulation of organic matter. The woodland represents a potentially sustainable option for remediating a low value site with difficult access that does not involve removal of the contaminated material to a landfill or making a permanent inert cover.     

Source-separated municipal solid waste compost application to Swiss chard and basil

A growth room experiment was conducted to evaluate the bioavailability of Cu, Mn, Zn, Ca, Fe, K, Mg, P, S, As, B, Cd, Co, Cr, Hg, Mo, Na, Ni, Pb, and Se from a sandy loam soil amended with source-separated municipal solid waste (SSMSW) compost. Basil (Ocimum basilicum L.) and Swiss chard (Beta vulgaris L.) were amended with 0, 20, 40, and 60% SSMSW compost to soil (by volume) mixture. Soils and compost were sequentially extracted to fractionate Cu, Pb, and Zn into exchangeable (EXCH), iron- and manganese-oxide-bound (FeMnOX), organic-matter (OM), and structurally bound (SB) forms. Overall, in both species, the proportion of Cu, Pb, and Zn levels in different fractions followed the sequence: SB > OM > FeMnOX > EXCH for Cu; FeMnOX = SB > OM > EXCH for Pb; and FeMnOX > SB = EXCH > OM for Zn. Application of SSMSW compost increased soil pH and electrical conductivity (EC), and increased the concentration of Cu, Pb, and Zn in all fractions, but not EXCH Pb. Basil yields were greatest in the 20% treatment, but Swiss chard yields were greater in all compost-amended soils relative to the unamended soil. Basil plants in 20 or 40% compost treatments reached flowering earlier than plants from other treatments. Additions of SSMSW compost to soil altered basil essential oil, but basil oil was free of metals. The results from this study suggest that mature SSMSW compost with concentrations of Cu, Pb, Mo, and Zn of 311, 223, 17, and 767 mg/kg, respectively, could be used as a soil conditioner without phytotoxic effects on agricultural crops and without increasing the normal range of Cu, Pb, and Zn in crop tissue. However, the long-term effect of the accumulation of heavy metals in soils needs to be carefully considered.     

Arsenic, cadmium, and lead in California cropland soils: role of phosphate and micronutrient fertilizers

Phosphate and micronutrient fertilizers contain potentially harmful trace elements, such as arsenic (As), cadmium (Cd), and lead (Pb). We investigated if application of these fertilizer increases the As, Cd, and Pb concentrations of the receiving soils. More than 1000 soil samples were collected in seven major vegetable production regions across California. Benchmark soils (no or low fertilizer input) sampled in 1967 and re-sampled in 2001 served as a baseline. Soils were analyzed for total concentrations of As, Cd, Pb, P, and Zn. The P and Zn concentrations of the soils were indicators of P fertilizer and micronutrient inputs, respectively. Results showed that the concentrations of these elements in the vegetable production fields in some production areas of California had been shifted upward. Principal component analysis and cluster analysis showed that the seven production areas could be sorted into three categories: (i) enrichment of As, Cd, and Pb, which was associated with the enrichment of P and Zn in one of the seven areas surveyed; (ii) enrichment of As, which was associated with enrichment of Zn in two of the seven areas surveyed; and (iii) no remarkable correlation between enrichment of As, Cd, and Pb and enrichment of P and Zn in the other four areas surveyed.     

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.