The availability of copper in soils historically amended with sewage sludge, manure, and compost

Metals in soils amended with sewage sludge are typically less available compared with those in soils spiked with soluble metal salts. However, it is unclear if this difference remains in the long term. A survey of copper (Cu) availability was made in soils amended with sewage sludge, manure, and compost, collectively named organic amendments. Paired sets of amended and control soils were collected from 22 field trials where the organic amendments had aged up to 112 yr. Amended soils had higher total Cu concentrations (range, 2-220 mg Cu kg; median, 15 mg Cu kg) and organic C (range, 1-16 g kg; median, 4 g kg) than control soils. All samples were freshly spiked with CuCl, and the toxicity of added Cu to barley was compared between amended and control soils. The toxicity of added Cu was significantly lower in amended soils than in control soil in 15 sets by, on average, a factor of 1.4, suggesting that aged amendments do not largely increase Cu binding sites. The fraction of added Cu that is isotopic exchangeable Cu (labile Cu) was compared between control soils freshly spiked with CuCl and amended soils with both soils at identical total Cu concentrations. Copper derived from amendments was significantly less labile (on average 5.9-fold) than freshly added Cu in 18 sets of soils. This study shows that Cu availability after long-term applications of organic amendments is lower than that of freshly added Cu salts, mainly because of its lower availability in the original matrix and ageing reactions than because of increased metal binding sites in soil.     

Availability of arsenic, copper, lead, thallium, and zinc to various vegetables grown in slag-contaminated soils

To anticipate a possible hazard resulting from the plant uptake of metals from slag-contaminated soils, it is useful to study whether vegetables exist that are able to mobilize a given metal in the slag to a larger proportion than in an uncontaminated control soil. For this purpose, we studied the soil to plant transfer of arsenic, copper, lead, thallium, and zinc by the vegetables bean (Phaseolus vulgaris L. 'dwarf bean Modus'), kohlrabi (Brassica oleracea var. gongylodes L.), mangold (Beta vulgaris var. macrorhiza ), lettuce (Lactuca sativa L. 'American gathering brown'), carrot (Daucus carota L. 'Rotin', 'Sperlings's'), and celery [Apium graveiolus var. dulce (Mill.) Pers.] from a control soil (Ap horizon of a Entisol) and from a contaminated soil (1:1 soil-slag mixtures). Two types of slags were used: an iron-rich residue from pyrite (FeS2) roasting and a residue from coal firing. The metal concentrations in the slags, soils, and plants were used to calculate for each metal and soil-slag mixture the plant-soil fractional concentration ratio (CRfractional,slag), that is, the concentration ratio of the metal that results only from the slag in the soil. With the exception of TI, the resulting values obtained for this quantity for As, Cu, Pb, and Zn and for all vegetables were significantly smaller than the corresponding plant-soil concentration ratios (CRcontrol soil) for the uncontaminated soil. The results demonstrate quantitatively that the ability of a plant to accumulate a given metal as observed for a control soil might not exist for a soil-slag mixture, and vice versa.     

Cadmium, copper, nickel, and zinc availability in a biosolids-amended piedmont soil years after application

Concerns over the possible increase in phytoavailability of biosolids-applied trace metals to plants have been raised based on the assumption that decomposition of applied organic matter would increase phytoavailability. The objectives of this study were to assess the effect of time on chemical extractability and concentration of Cd, Cu, Ni, and Zn in plants on plots established by a single application of biosolids with high trace metals content in 1984. Biosolids were applied to 1.5 by 2.3 m confined plots of a Davidson clay loam (clayey, kaolinitic, thermic Rhodic Kandiudults) at 0, 42, 84, 126, 168, and 210 Mg ha(-1). The highest biosolids application supplied 4.5, 760, 43, and 620 kg ha(-1) of Cd, Cu, Ni, and Zn, respectively. Radish (Raphanus sativus L.), romaine lettuce (Lactuca sativa L. var. longifolia), and barley (Hordeum vulgare L.) were planted at the site for 3 consecutive years, 17 to 19 yr after biosolids application. Extractable Cd, Cu, Ni, and Zn (as measured by DTPA, CaCl(2,) and Mehlich-1) were determined on 15-cm depth samples from each plot. The DTPA-extractable Cu and Zn decreased by 58 and 42%, respectively, 17 yr after application despite a significant reduction in organic matter content. Biosolids treatments had no significant effect on crop yield. Plant tissue metal concentrations increased with biosolids rate but were within the normal range of these crops. Trace metal concentrations in plants generally correlated well with the concentrations extracted from soil with DTPA, CaCl(2), and Mehlich-1. Metal concentrations in plant tissue exhibited a plateau response in most cases. The uptake coefficient values generated for the different crops were in agreement with the values set by the Part 503 Rule.     

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.     

Dissolution of trace element contaminants from two coastal plain soils as affected by pH

Trace element mobility in soils depends on contaminant concentration, chemical speciation, water movement, and soil matrix properties such as mineralogy, pH, and redox potential. Our objective was to characterize trace element dissolution in response to acidification of soil samples from two abandoned incinerators in the North Carolina Coastal Plain. Trace element concentrations in 11 soil samples from both sites ranged from 2 to 46 mg Cu kg(-1), 3 to 105 mg Pb kg(-1), 1 to 102 mg Zn kg(-1), 3 to 11 mg Cr kg(-1), < 0.1 to 10 mg As kg(-1), and < 0.01 to 0.9 mg Cd kg(-1). Acidified CaCl2 solutions were passed through soil columns to bring the effluent solution to approximately pH 4 during a 280-h flow period. Maximum concentrations of dissolved Cu, Pb, and Zn at the lowest pH of an experiment (pH 3.8-4.1) were 0.32 mg Cu L(-1), 0.11 mg Pb L(-1), and 1.3 mg Zn L(-1) for samples from the site with well-drained soils, and 0.25 mg Cu L(-1), 1.2 mg Pb L(-1), and 1.4 mg Zn L(-1) for samples from the site with more poorly drained soils. Dissolved Cu concentration at pH 4 increased linearly with increasing soil Cu concentration, but no such relationship was found for Zn. Dissolved concentrations of other trace elements were below our analytical detection limits. Synchrotron X-ray absorption near edge structure (XANES) spectroscopy showed that Cr and As were in their less mobile Cr(III) and As(V) oxidation states. XANES analysis of Cu and Zn on selected samples indicated an association of Cu(II) with soil organic matter and Zn(II) with Al- and Fe-oxides or franklinite.     

Root penetration of sealing layers made of fly ash and sewage sludge

Fly ash and sewage sludge are suggested materials for constructing sealing layers covering mine tailings impoundments. Little is known, however, of their effect on vegetation or resistance to root penetration. We investigate: (i) the ability of different plant species to grow in sealing layers comprising fly ash and sewage sludge, (ii) the impact on plant growth of freshly hardened fly ash compared to aged and leached ash, and (iii) the plant stress response to fly ashes of different properties. A 6-mo greenhouse study using birch (Betula pendula Roth.), Scots pine (Pinus sylvestris L.), Kentucky bluegrass (Poa pratensis L.), and willow (Salix viminalis L.) demonstrated that no roots could grow into a compacted layer consisting only of ash, while a 6:4, ash-sludge mixture admitted roots into the upper part and a 1:9, ash-sludge mixture was totally penetrated (to 15 cm in depth) by roots of willow and Scots pine. Freshly hardened ash prevented root growth more effectively than aged ash did, as was observed in tests using reed canarygrass (Phalaris arundinacea L.) and pea (Pisum sativum L.). Furthermore, extracts of highly alkaline ash were more toxic to pea in a 48-h toxicity test than less alkaline ash was. However, stress responses to diluted ash extracts of lower pH, measured as enzyme capacities in dwarf bean (Phaseolus vulgaris L.), were more related to the metal and ion contents. Root penetration of sealing layers is most effectively prevented if little sewage sludge is added, and if ash of high alkalinity is chosen.     

Pesticide applications of copper on perennial crops in California, 1993 to 1998

Inorganic copper is used as a broad-spectrum fungicide and bacteriocide on a variety of agricultural crops. After application, the copper residue typically accumulates in the upper 15 cm of soil. Data from the California Pesticide Use Reports were used to estimate the augmentation of copper in the soil that resulted from pesticide applications for the six years from 1993 to 1998 on 12 crops that are grown without rotation. The estimated mean mg Cu kg(-1) soil added to the upper 15 cm during the six years was the following: walnut (Juglans regia L.), 28; peach [Prunus persica (L.) Batsch var. persica], 22; nectarine [Prunuspersica (L.) Batsch var. nucipersica (Suckow) C.K. Schneid], 19; cherry (Pseudolmedia oxyphyllaria Donn. Sm.), 18; rice (Orvza sativa L.), 16; apricot (Prunus armeniaca L.), 11; orange [Citrus sinensis (L.) Osbeck) and plum (Prunus domestica L. subsp. domestica ), 9; lemon [Citrus limon (L.) Burm.f.] and almond [Prunus dulcis (Mill.) D.A. Webb], 6; pear (Pyrus communis L.), 4; and grape (Vitis vinifera L.), 3. In addition, for the first five of these crops, we estimated the area that was treated with each level of kg Cu ha(-1). For example, for walnut orchards, we estimated that 12 500 ha, or 17% of the planted area, was treated with a quantity of Cu that would increase the total concentration of Cu in the upper 15 cm of soil by at least 50 mg Cu kg(-1) soil. A comparison of the amount of Cu per unit planted area that was applied in the first and second half of the study indicated that the intensity of copper use is either relatively constant or increasing, depending on the crop. The findings are discussed in relation to the potential effect of continued long-term use of Cu pesticides on soil sustainability.     

In situ accumulation of copper, chromium, nickel, and zinc in soils used for long-term waste water reclamation

We studied the long-term in situ accumulation of Cu, Cr, Ni, and Zn in the soil profile of a large-scale effluent recharge basin after 24 yr of operation in a wastewater reclamation plant using the Soil Aquifer System approach in the Coastal Plain of Israel. The objective was to quantify metals accumulation in the basin's soil profile, clarify retention mechanisms, and calculate material balances and metal removal efficiency as the metal loads increase. Effluent recharge led to measurable accumulation, relative to the pristine soil, of Ni and Zn in the 0- to 4-m soil profile, with concentration increases of 0.3 to 1.3 mg kg(-1) and 2.9 to 6.4 mg kg(-1), respectively. Copper accumulated only in the 0- to 1-m top soil layer, with concentration increase of 0.28 to 0.76 mg kg(-1). Chromium concentration increased by 3.1 to 7.3 mg kg(-1) in the 0- to 1-m horizon and 0.9 to 2.3 mg kg(-1) at deeper horizons. Sequential selective extraction showed Cu tended to be preferentially retained by Fe oxides and organic matter (OM), Cr by OM, Ni by OM, and carbonate and Zn by carbonate. The average total retained amounts of Cu, Cr, Ni, and Zn were 0.7 +/- 1.0, 13.6 +/- 4.8, 4.3 +/- 3.6, and 28.7 +/- 5.4 g per a representative unit soil slab (1 m(2) x 4 m) of the basin, respectively. This amounts to 3.6 +/- 4.9%, 79.5 +/- 28.0%, 8.0 +/- 6.9%, and 9.3 +/- 1.8% of the Cu, Cr, Ni, and Zn loads, respectively, applied during 24 yr of effluent recharge (total of approximately 1880 m effluent load). The low long-term overall removal efficiency of the metals from the recharged effluent in the top horizon may be due to the metals' low concentrations in the recharged effluent and the low adsorption affinity and retention capacity of the sandy soil toward them. This leads to attainment of a quasi-equilibrium and a steady state in element distribution between the recharged effluent solution and the soil after few years of recharge and relatively small cumulative effluent loadings.     

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.     

Trace element changes in soil after long-term cattle manure applications

Manure application supplies plant nutrients, but also leads to trace element accumulation in soil. This study investigated total and EDTA-extractable B, Cd, Co, Cu and Zn in soil after 25 annual manure applications. The residual effect of 14 annual manure applications followed by 11 yr with no applications was also investigated. Manure was applied at 0, 30, 60 and 90 Mg ha(-1) yr(-1) (wet weight) under rainfed (treatments Mr0, Mr30, Mr60, and Mr90) and at 0, 60, 120 and 180 Mg ha(-1) yr(-1) under irrigated conditions (Mi0, Mi60, Mi120, and Mi180). The manure applications had no significant effect on soil B, Cd and Co content under both rainfed and irrigated conditions, but significantly increased total Cu and Zn content under irrigated conditions with Zn in Mi120 and Mi180 reaching the lower maximum concentration (MAC) level set by the European Community. Manure application also significantly increased EDTA-extractable Cd and Zn content in soil. Up to 27% of the total Cd (0.156 mg kg(-1)) and 21% of total Zn (38 mg kg(-1)) are found in EDTA-extractable form (Mi180 at 0-15 cm). EDTA-extractable Cd and Zn content was also significantly elevated in the irrigated residual plots due to the higher manure rates used. Thus, the impacts of cattle manure application on trace elements in soil are long lasting. Elevated Cd and Zn are a concern as other studies have linked them with certain types of cancers and human illnesses.     

蓖麻（Ric inus communist L.）对锰矿区土壤中重金属累积特性的研究

为探讨蓖麻（Ricinus communist L.）对锰矿区土壤生态修复及能源化利用潜力,将不同品种蓖麻湘蓖1号和淄蓖7号播种在锰尾矿库土壤上,进入生殖生长阶段时采收全株,测定栽植土壤及植株根、茎、叶中5种重金属元素含量。结果显示：土壤中Mn平均含量最高达7884.96 mg＆#183;kg-1,超过国家规定的土壤环境质量域级标准6.5倍;湘蓖1号不同器官的Mn浓度从高至低为根＆gt;叶＆gt;茎,淄蓖7号不同器官Mn含量叶＆gt;茎＆gt;根,其叶中Mn平均浓度最高为765.43 mg＆#183;kg-1,较湘蓖1号叶中的平均含量高出79.53%, Pb、Cu、Cr含量及叶/根比值均大于湘蓖1号;植株体内重金属含量与土壤中重金属浓度的相关分析表明,重金属的积累量和转移量,受到土壤中几种重金属元素的共同影响。结果说明：2个品种的蓖麻均可以作为锰矿区能源化修复利用,对重金属的吸收和转运在品种间存在差异,淄蓖7号地上部分对重金属的迁移能力强于湘蓖1号。     

Arsenic accumulation in the hyperaccumulator Chinese brake and its utilization potential for phytoremediation

The unique property of arsenic hyperaccumulation by the newly discovered Chinese brake (Pteris vittata L.) fern is of great significance in the phytoremediation of arsenic-contaminated soils. The objectives of this study were to (i) examine arsenic accumulation characterized by its distribution pattern in Chinese brake, and (ii) assess the phytoextraction potential of the plant. Young ferns with five or six fronds were transferred to an arsenic-contaminated soil containing 98 mg As kg-1 and grown for 20 wk in a greenhouse. At harvest, the Chinese brake produced a total dry biomass of 18 g plant-1. Arsenic concentration in the fronds was 6000 mg kg-1 dry mass after 8 wk of transplanting, and it increased to 7230 mg kg-1 after 20 wk with a bioconcentration factor (ratio of plant arsenic concentration to water-soluble arsenic in soil) of 1450 and a translocation factor (ratio of arsenic concentration in shoot to that in root) of 24. The arsenic concentrations increased as the fronds aged, with the old fronds accumulating as much as 13,800 mg As kg-1. Most (approximately 90%) of the arsenic taken up by the Chinese brake was transported to the fronds, with the lowest arsenic concentrations in roots. About 26% of the initial soil arsenic was removed by the plant after 20 wk of transplanting. Our data suggest that the arsenic hyperaccumulating property of the Chinese brake could be exploited on a large scale to remediate arsenic contaminated soils.     

Dredged Illinois River sediments: plant growth and metal uptake

Sedimentation of the Illinois River in central Illinois has greatly diminished the utility and ecological value of the Peoria Lakes reach of the river. Consequently, a large dredging project has been proposed to improve its wildlife habitat and recreation potential, but disposal of the dredged sediment presents a challenge. Land placement is an attractive option. Previous work in Illinois has demonstrated that sediments are potentially capable of supporting agronomic crops due to their high natural fertility and water holding capacity. However, Illinois River sediments have elevated levels of heavy metals, which may be important if they are used as garden or agricultural soil. A greenhouse experiment was conducted to determine if these sediments could serve as a plant growth medium. A secondary objective was to determine if plants grown on sediments accumulated significant heavy metal concentrations. Our results indicated that lettuce (Lactuca sativa L.), barley (Hordeum vulgare L.), radish (Raphanus sativus L.), tomato (Lycopersicon lycopersicum L.), and snap bean (Phaseolus vulagaris L. var. humillis) grown in sediment and a reference topsoil did not show significant or consistent differences in germination or yields. In addition, there was not a consistent statistically significant difference in metal content among tomatoes grown in sediments, topsoil, or grown locally in gardens. In the other plants grown on sediments, while Cd and Cu in all cases and As in lettuce and snap bean were elevated, levels were below those considered excessive. Results indicate that properly managed, these relatively uncontaminated calcareous sediments can make productive soils and that metal uptake of plants grown in these sediments is generally not a concern.     

Surface runoff losses of copper and zinc in sandy soils

Increased anthropogenic inputs of Cu and Zn in soils have caused considerable concern relative to their effect on water contamination. Copper and Zn contents in surface soil directly influence the movement of Cu and Zn. However, minimal information is available on runoff losses of Cu and Zn in agricultural soils, and soil-extractable Cu and Zn in relation to runoff water quality. Field experiments were conducted in 2001 to study dissolved Cu and Zn losses in runoff in Florida sandy soils under commercial citrus and vegetable production and the relationship between soil-extractable Cu and Zn forms and dissolved Cu and Zn concentrations in runoff water. Five extraction methods were compared for extracting soil available Cu and Zn. Concentrations of dissolved Cu and Zn in runoff were measured and runoff discharge was monitored. Mean dissolved Cu in field runoff water was significantly correlated with the extractable Cu obtained only by 0.01 mol L(-1) CaCl2, Mehlich 1, or DTPA-TEA methods. Dissolved Zn in runoff water was only significantly correlated with extractable Zn by 0.01 mol L(-1) CaCl2. The highest correlations to dissolved Cu in runoff were obtained when soil-available Cu was extracted by 0.01 mol L(-1) CaCl2. The results indicate that 0.01 mol L(-1) CaCl2-extractable Cu and Zn are the best soil indexes for predicting readily released Cu and Zn in the sandy soils. Both runoff discharge and 0.01 mol L(-1) CaCl2-extractable Cu and Zn levels had significant influences on Cu and Zn loads in surface runoff.     

Potential risks of copper, zinc, and cadmium pollution due to pig manure application in a soil-rice system under intensive farming: a case study of Nanhu, China

Heavy metal (copper [Cu], zinc [Zn], and cadmium [Cd]) pollution of soils from pig manures in soil-rice ( L.) systems under intensive farming was investigated, taking Nanhu, China, as the case study area. Two hundred pig manures and 154 rice straws, brown rice samples, and corresponding surface soil (0-15 cm) samples were collected in paddy fields from 150 farms in 16 major villages within the study area. The mean Cu and Zn concentrations in pig manures consistently exceeded the related standard. About 44 and 60% of soil samples exceed the Chinese Soil Cu and Cd Environmental Quality Standards, respectively. The concentration of Cu, Zn, and Cd in brown rice did not exceed the Chinese Food Hygiene Standard. There was a significant positive correlation between total Cu and Zn contents in soil and application rate of pig manures. Strong correlation was observed between the extractable Cu, Zn, and Cd in soil and the Cu, Zn, and Cd contents in the brown rice. The spatial distribution maps of Cu and Zn concentrations in brown rice, straw, and extractable soil Cu and Zn concentration also showed similar geographical trends. Further analyses on heavy metals loading flux and accumulation rates from pig manure applied suggested that Cu and Cd contents in soil currently have already exceeded the maximum permissible limit, and Zn, if still at current manure application rates, will reach the ceiling concentration limits in 9 yr. This study assists in understanding the risk of heavy metals accumulating from pig manure applications to agricultural soils.     

Influence of soil properties and aging on the toxicity of copper on compost worm and barley

Influence of soil properties and aging on Cu partitioning and toxicity was assessed on 10 artificial soils constituted using a statistical design considering pH (5.5 and 7.5), organic matter (1-30% [w/w]), and clay content (5-35% [w/w]). Total Cu as well as water-, CaCl2-, and diethylene triamine pentaacetic acid (DTPA)-extracted Cu fractions were determined for each soil mixture. Ecotoxic effect was assessed by determining growth inhibition of barley (Hordeum vulgare L.) and compost worm (Eisenia fetida) mortality. Analyses were repeated after a 16-wk aging period of the soils at pH 7.5 (8 x 2-wk wetting and drying cycle). Results indicated that pH was the main factor controlling Cu partitioning, ahead of organic matter and clay content. Calcium chloride (0.5 M)-extracted Cu fractions showed the best correlation with toxic responses (r = 0.55-0.66; p < 0.05), while total and DTPA-extracted Cu concentrations could not explain differences in toxicity. Direct regressions between toxicity and soil properties (pH, organic matter, and clay content) provided better explanation of variance: r2= 0.50 (p = 0.00006) for compost worm mortality, r2= 0.77 (p < 0.00001) for barley shoot inhibition, and r2= 0.92 (p < 0.00001) for barley root inhibition. Copper toxicity was mainly influenced by pH and, to a lesser extent, by organic matter and clay content. Aging in organic soils revealed a slight reduction in ecotoxicity while an increase was observed in soils with low organic matter content. Further investigation using longer aging periods would be necessary to assess the significance of this observation.     

Fate of biosolids trace metals in a dryland wheat agroecosystem

Biosolids land application for beneficial reuse applies varying amounts of trace metals to soils. Measuring plant-available or total soil metals is typically performed to ensure environmental protection, but these techniques do not quantify which soil phases play important roles in terms of metal release or attenuation. This study assessed the distribution of Cd, Cr, Cu, Mo, Ni, Pb, and Zn associated with soluble/exchangeable, specifically adsorbed/carbonate-bound, amorphous Mn hydroxyoxide-bound, amorphous Fe hydroxyoxide-bound, organically complexed, and residual inorganic phases. Biosolids were applied every 2 yr from 1982 to 2002 (except in 1998) at rates of 0, 6.7, 13.4, 26.8, and 40.3 dry Mg biosolids ha(-)(1) to 3.6- by 17.1-m plots. In 2003, 0- to 20-cm and 20- to 60-cm soil depths were collected and subjected to 4 mol L(-1) HNO(3) digestion and sequential extraction. Trace metals were concentrated in the 0- to 20-cm depth, with no significant observable downward movement using 4 mol L(-1) HNO(3) or sequential extraction. The sequential extraction showed nearly all measurable Cd present in relatively mobile forms and Cr, Cu, Mo, Ni, Pb, and Zn present in more resistant phases. Biosolids application did not affect Cd or Cr fractionation but did increase relatively immobile Cu, Mo, and Zn phases and relatively mobile Cu, Ni, and Pb pools. The mobile phases have not contributed to significant downward metal movement. Long-term, repeated biosolids applications at rates considered several times greater than agronomic levels should not significantly contribute to downward metal transport and ground water contamination for soils under similar climatic conditions, agronomic practices, and histories.     

TCLP法评价钢铁工业区周边土壤重金属生态环境风险

采用土壤随机布点法,采集某钢铁工业区周边34个土壤样品,利用美国TCLP法对钢铁工业区周边土壤重金属（Cu、 Zn、 Pb、 Cd）有效态进行实验分析和生态风险评价。结果表明, Cu、 Zn、 Pb、 Cd有效态含量分别在0.87~57.7 mg/kg、5.20~1338 mg/kg、1.09~379 mg/kg、1.15×10-3~69.9×10-3 mg/kg之间,钢铁工业区土壤不同程度地受到重金属的污染,其中以Zn污染最为严重。内梅罗污染指数评价中,处于安全水平的点位仅占17.6%,受到污染的点位占55.9%。其中,轻污染占20.6%,中污染占2.9%,重污染占32.4%。     

Soil carbon dioxide emission and carbon content as affected by irrigation, tillage, cropping system, and nitrogen fertilization

Management practices can influence soil CO(2) emission and C content in cropland, which can effect global warming. We examined the effects of combinations of irrigation, tillage, cropping systems, and N fertilization on soil CO(2) flux, temperature, water, and C content at the 0- to 20-cm depth from May to November 2005 at two sites in the northern Great Plains. Treatments were two irrigation systems (irrigated vs. non-irrigated) and six management practices that contained tilled and no-tilled malt barley (Hordeum vulgaris L.) with 0 to 134 kg N ha(-1), no-tilled pea (Pisum sativum L.), and a conservation reserve program (CRP) planting applied in Lihen sandy loam (sandy, mixed, frigid, Entic Haplustolls) in western North Dakota. In eastern Montana, treatments were no-tilled malt barley with 78 kg N ha(-1), no-tilled rye (Secale cereale L.), no-tilled Austrian winter pea, no-tilled fallow, and tilled fallow applied in dryland Williams loam (fine-loamy, mixed Typic Argiborolls). Irrigation increased CO(2) flux by 13% compared with non-irrigation by increasing soil water content in North Dakota. Tillage increased CO(2) flux by 62 to 118% compared with no-tillage at both places. The flux was 1.5- to 2.5-fold greater with tilled than with non-tilled treatments following heavy rain or irrigation in North Dakota and 1.5- to 2.0-fold greater with crops than with fallow following substantial rain in Montana. Nitrogen fertilization increased CO(2) flux by 14% compared with no N fertilization in North Dakota and cropping increased the flux by 79% compared with fallow in no-till and 0 kg N ha(-1) in Montana. The CO(2) flux in undisturbed CRP was similar to that in no-tilled crops. Although soil C content was not altered, management practices influenced CO(2) flux within a short period due to changes in soil temperature, water, and nutrient contents. Regardless of irrigation, CO(2) flux can be reduced from croplands to a level similar to that in CRP planting using no-tilled crops with or without N fertilization compared with other management practices.     

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.