Fate and effect of zinc from tire debris in soil

Tire debris contains significant quantities of zinc (Zn), and there is concern about the diffuse Zn contamination of soils from tire wear. An experiment was set up to quantify the fate and effect of Zn from tire debris in soil. Two different soils were mixed with the <100-microm fraction of car and truck tire debris (25 g kg(-1) soil) or zinc sulfate (ZnSO4) as a reference. Soils were transferred to soil columns with free drainage and placed outdoors for 11 months. Leachates of the tire debris amended soils did not contain significantly (P>0.05) more Zn than control soils except for a 3-fold increase in one soil amended with cartire debris. The increase in Zn leaching due to tire debris was only 3% of the corresponding increase in the ZnSO4 treatment at the same total Zn in soil. Tire debris application increased the soil nitrification potential, whereas ZnSO4 application, at corresponding or smaller total Zn concentration, decreased nitrification potential. An increase in soil pH was observed in all soils treated with tire debris and explains the increased nitrification potential. About 10-40% of the Zn from tire debris was isotopically exchangeable in soil sampled after 1 year weathering. It is concluded that a significant fraction of Zn is released from the rubber matrix within 1 year, but the parallel increase in soil pH limits the mobilization of Zn in soil.     

Kinetics of Zn release in soils and prediction of Zn concentration in plants using diffusive gradients in thin films

Effective concentrations (CE) of Zn measured by the technique of DGT (diffusive gradients in thin films) were compared, along with total concentrations of Zn and the concentrations of Zn in soil solutions, to Zn concentrations in plants. Soils variously contaminated with Zn were collected in the vicinity of two galvanized electrical transmission towers (pylons) and two motorway crash barriers. Lepidium sativum was grown in each soil and in corresponding control soils amended with ZnCl2 to similar total Zn concentrations. CE, concentrations in soil solution, and total Zn were measured in all soils, and total Zn was measured in the plant shoots. The CE values, soil solution Zn, and shoot Zn concentrations were all larger in ZnCl2 amended soils than in field contaminated soils at corresponding total Zn. Correlations between the concentration of Zn in the plants and the measured soil parameter followed the order CE > soil solution > total Zn. The low scatter in the plot of log plant concentration versus log CE revealed a relationship with two distinct features. Plant Zn was between 100 and 300 mg/kg up to an effective Zn concentration of about 2 mg/L, above which plant Zn increased steadily with increasing CE. Use of a dynamic model to interpret the DGT measurement suggests that the intrinsic rate of release of Zn from solid phase to solution, expressed as a rate constant, is much higher for soils that receive fresh supplies of Zn. This finding provides a mechanistic basis for reconciling laboratory experiments, where metal is freshly amended, to data obtained in the field. The potential of DGT as a surrogate for metal availability to plants is further confirmed by this work.     

Zinc toxicity to nitrification in soil and soilless culture can be predicted with the same biotic ligand model

The inhibitory effect of Zn on the nitrification process in ZnCl2 spiked soils (12 soils, pH range 4.8-7.5) was compared to toxic effects of Zn on the nitrification by Nitrosospira sp. in soilless solutions with varying pH (pH 6-8) and ionic composition. The nitrification was reduced by 20% at Zn solution concentrations (EC20) ranging between 7 and 1200 microM Zn in the soil pore water and between 5 and 150 microM Zn in the soilless solutions. Protective effects of H+, Ca2+, and Mg2+ against Zn2+ toxicity were observed in both systems. Zinc speciation was determined, and 60-90% of the Zn in the soils and 35-80% of the Zn in the soilless solutions was present as Zn2+. A biotic ligand model and a Freundlich-type model, incorporating the competition of Zn2+ ions with H+, Ca2+, and Mg2+ for binding on the biotic ligands, were used to model the results. The Zn2+ activities resulting in 20% reduction of the nitrification were well predicted using the same parameters for both (soil and soilless) systems, indicating that microorganisms in soil are exposed to zinc through the free zinc ion in soil pore water.     

Copper dynamics and impact on microbial communities in soils of variable organic status

The effect of soil organic status on copper impact was investigated by means of a microcosm study carried out on a vineyard soil that had been amended with varying types of organic matter during a previous long-term field experiment. Soil microcosms were contaminated at 250 mg Cu kg(-1) and incubated for 35 days. Copper distribution and dynamics were assessed in the solid matrix by a sequential extraction procedure and in the soil solution by measuring total and free exchangeable copper concentrations. Copper bioavailability was also measured with a whole-cell biosensor. Modifications of microbial communities were assessed by means of biomass-C measurements and characterization of genetic structure using ARISA (automated-ribosomal-intergenic-spacer-analysis). The results showed that copper distribution, speciation, and bioavailability are strongly different between organically amended and nonamended soils. Surprisingly, in solution, bioavailable copper correlated with total copper but not with free copper. Similarly the observed differential copper impact on micro-organisms suggested that organic matter controlled copper toxicity. Bacterial-ARISA modifications also correlated with the estimated metal bioavailability and corresponded to the enrichment of the Actinobacteria. Contrarily, biomass-C and fungal-ARISA measurements did not relate trivially to copper speciation and bioavailability, suggesting that the specific composition of the indigenous-soil communities controls its sensitivity to this metal.     

镉胁迫对不同植烟土壤硝化速率及N2O排放的影响

为明确镉(Cd)胁迫对不同植烟土壤的硝化速率及氧化亚氮(N₂O)排放的影响,采用外源镉添加试验,设置两个 Cd浓度梯度(10和100mg/kg),以探究Cd胁迫下中性(中性土1和2)和酸性(酸性土1和2)植烟土壤的净硝化速率以及N₂O排放特征。结果表明:1)随培养时间增加,植烟土壤铵态氮含量逐渐减少,而硝态氮含量逐渐增加,且低Cd胁迫和高Cd胁迫均未显著改变这一变化趋势;2)植烟土壤净硝化速率在培养前期(1~7 d)发生较大波动变化,Cd胁迫明显增加了酸性土1在第1天的净硝化速率;3)整体上各处理酸性土的N₂O排放速率和累积排放量高于中性土,高Cd胁迫增加了酸性土1的N₂O初始排放速率,培养结束后酸性土1的N₂O累积排放量达355.42μg/kg;4)各植烟土壤N₂O排放速率和累积排放量与土壤pH和全氮含量极显著负相关,而与有机质和铵态氮含量极显著正相关。本研究结果表明植烟土壤的N₂O排放受土壤酸碱性和氮底物的影响,酸性土的N₂O累积排放量高于中性土,且高Cd胁迫增加其N₂O排放量,后续可通过土壤酸化改良以达到N₂O减排目的。     

Predicting arsenic solubility in contaminated soils using isotopic dilution techniques

An isotopic dilution assay was developed to measure radiolabile As concentration in a diverse range of soils (pH 3.30-7.62; % C = 1.00-6.55). Soils amended with 50 mg of As kg(-1) (as Na2HAsO4 x 7H2O) were incubated for over 800 d in an aerated "microcosm" experiment. After 818 d, radiolabile As ranged from 27 to 57% of total applied As and showed a pH-dependent increase above pH 6. The radiolabile assay was also applied to three sets of soils historically contaminated with sewage sludge or mine-spoil. Results reflected the various geochemical forms in which the arsenic was present. On soils from a sewage disposal facility, radiolabile arsenate ranged from 3 to 60% of total As; mean lability was lower than in the equivalent pH range of the microcosm soils, suggesting occlusion of As into calcium phosphate compounds in the sludge-amended soils. In soils from mining areas in the U.K. and Malaysia, radiolabile As accounted for 0.44-19% of total As. The lowest levels of lability were associated with extremely large As concentrations, up to 17,000 mg kg(-1), from arsenopyrite. Soil pore water was extracted from the microcosm experiment and speciated using "GEOCHEM". The solid<==>solution equilibria of As in the microcosm soils was described by a simple model based on competition between HAsO4(2-) and HPO4(2-) for "labile" adsorption sites.     

Low δ(18)O Values of Nitrate Produced from Nitrification in Temperate Forest Soils

Analyses of δ(18)O of nitrate (NO(3)(-)) have been widely used in partitioning NO(3)(-) sources. However the δ(18)O value of NO(3)(-) produced from nitrification (microbial NO(3)(-)) is commonly estimated using the δ(18)O of environmental water and molecular oxygen in a 2:1 ratio. Here our laboratory incubation of nine temperate forest soils across a 1500 m elevation gradient demonstrates that microbial NO(3)(-) has lower δ(18)O values than the predicted using the 2:1 ratio (by 5.2-9.5‰ at low elevation sites), in contrast to previous reports showing higher δ(18)O values (up to +15‰) than their predicted values. Elevated δ(18)O values of microbial NO(3)(-) were observed at high elevation sites where soil was more acidic, perhaps due to accelerated O-exchange between nitrite, an intermediate product of nitrification, and water. Lower δ(18)O of microbial NO(3)(-) than the predicted and from previous observations suggests that the contribution of anthropogenic N inputs, such as fertilizer and atmospheric deposition, to a given ecosystem and the progress of denitrification in nitrogen removal are greater than we know. More than half of the δ(18)O of stream NO(3)(-) lower than the predicted value along the elevation gradient also indicate the impropriety using the 2:1 ratio for differentiating NO(3)(-) sources.     

Evaluation of the acetylene-inhibition technique for the measurement of denitrification in grassland soils

The acetylene inhibition technique has been evaluated for its suitability for routine field measurements of denitrification in two soils under grass. Acetylene was introduced into the soil air by radial diffusion from probes inserted vertically into the soil and, using a soil cover, total denitrification was determined as the loss of nitrous oxide (N₂O) from the acetylene-treated soil. Acetylene concentrations of 0.1–1.0% (v/v), which are effective in inhibiting the reduction of N₂O, were established within 1–2 h of commencing the supply of acetylene to soil at field capacity; the N₂O flux equilibrated within the same period. Treatment and equilibration times were longer after rainfall on to a soil at field capacity and shorter in spring, summer and autumn when soil water content was less than field capacity. Spatial variability in N₂O flux from acetylene-treated soil was generally ±25% and was probably associated with variability in air-filled pore spaces in the soil. Repeated treatments, as required in routine measurements of denitrification, did not affect the distribution of soil inorganic N between NH₄+ and NO₃- which suggests that concurrent inhibition of nitrification by acetylene was not a significant constraint in the field application of the technique. The efficiency with which acetylene inhibits the reduction of N₂O was not affected by repeated treatments of soil nor was there any evidence for acetylene decomposition. Repeated treatments did not affect dry matter yield or mineral contents of herbage. The findings of this study suggest that the acetylene-inhibition technique may be applied to routine measurements of denitrification in both small and large plot studies of the fate of fertilizer N.     

Impact of black carbon in the extraction and mineralization of phenanthrene in soil

During the past century, increased biomass burning and fossil fuel consumption have drastically increased the input of black carbon (BC) into the environment, and that has been shown to influence the behavior of organic contaminants in soil. A study was conducted to investigate the effects of BC on the relationship between aqueous hydroxypropyl-beta-cyclodextrin (HPCD) extraction and microbial mineralization (bioaccessibility) of 14C-phenanthrene (10 mg kg(-1)) in four soils amended with 0, 0.1, 0.5, 1, 2.5, and 5% (% dry wt soil) activated charcoal, a type of BC. Mineralisation was monitored over 20 d incubation, within respirometric assays, using an inoculum containing a phenanthrene-degrading pseudomonad and compared to HPCD extraction (24 h) using 50 mM aqueous solution; analyses were conducted after 1, 25, 50, and 100 d soil-phenanthrene contact time. Statistical analyses revealed that for each soil the addition of BC led to significant (P < 0.001) reductions in both HPCD extractability and microbial mineralization. Linear correlations for BC concentrations of 0% (r2 = 0.95; slope = 0.89) and 0.1% (r2 = 0.67; slope = 0.95) revealed a highly significant (P < 0.01) relationship between HPCD extractability and total mineralization (20 d), indicating a direct prediction of phenanthrene bioaccessibility by HPCD. However, in soils amended with 0.5, 1, 2.5, and 5% BC exhibited r2 values ranging 0.51-0.13 and slopes of 2.19-12.73. This study has shown that BC strongly sorbs phenanthrene causing reductions in extractability and, to a lesser extent, bioaccessibility to degrading microorganisms.     

Biotransformation and accumulation of arsenic in soil amended with seaweed

For many coastal regions of the world, it has been common practice to apply seaweed to the land as a soil improver and fertilizer. Seaweed is rich in arsenosugars and has a tissue concentration of arsenic up to 100 micro/g g(-1). These arsenic species are relatively nontoxic to humans; however, in the environment they may accumulate in the soil and decompose to more toxic arsenic species. The aim of this study was to determine the fate and biotransformation of these arsenosugars in soil using HPLC-ICP-MS analysis. Data from coastal soils currently manured with seaweeds were used to investigate if arsenic was accumulating in these soils. Long-term application of seaweed increased arsenic concentrations in these soils up to 10-fold (0.35 mg of As kg(-1) for nonagronomic peat, 4.3 mg of As kg(-1) for seaweed-amended peat). The biotransformation of arsenic was studied in microcosm experiments in which a sandy (machair) soil, traditionally manured with seaweed, was amended with Laminaria digitata and Fucus vesiculosus. In both seaweed species, the arsenic occurs in the form of arsenosugars (85%). The application of 50 g of seaweed to 1 kg of soil leads to an increase of arsenic in the soils, and the dominating species found in the soil pore water were dimethylarsinic acid (DMA(V)) and the inorganic species arsenate (As(V)) and arsenite (As(III)) after the initial appearance of arsenosugars. A proposed decomposition pathway of arsenosugars is discussed in which the arsenosugars are transformed to DMA(V) and further to inorganic arsenic without appreciable amounts of methylarsonic acid (MA(V)). Commercially available seaweed-based fertilizers contain arsenic concentration between 10 and 50 mg kg(-1). The arsenic species in these fertilizers depends on the manufacturing procedure. Some contain mainly arsenosugars while others contain mainly DMA(V) and inorganic arsenic. With the application rates suggested by the manufacturers, the application of these fertilizers is 2 orders of magnitude lower than the maximum permissible sewage sludge load for arsenic (varies from 0.025 kg ha(-1) yr(-1) in Styria, Austria, to 0.7 kg ha(-1) yr(-1) in the U.K.), while a direct seaweed application would exceed the maximum arsenic load by at least a factor of 2.     

Adaptation of soil biological nitrification to heavy metals

The adaptive response of soil biological nitrification to Zn and Pb was assessed using an in situ method we have developed. The method is based on reinoculating a sterilized metal contaminated soil with the same soil that is either uncontaminated or has been incubated with metal. This approach excludes the potentially confounding effects of metal aging reactions in soils. We found added Zn concentrations which gave rise to a decrease in nitrification to 50% that of the uncontaminated soil (i.e. EC50) of 210 mg/kg for communities not previously exposed to Zn and 850 mg/kg for communities exposed to Zn for 17 months, indicating that significant adaptation of the community to Zn had occurred. Similarly, this protocol was able to demonstrate adaptation of soil biological nitrification to Pb, with EC50 values of 1960 and 3150 mg/kg for the unexposed and exposed treatments, respectively. Exposure of unadapted and adapted microbial communities to a combination of Zn and Cd showed that the presence of Cd did not lead to greater toxicity in either community. Adapted communities were not more sensitive to decreases in soil pH than unadapted communities. Prior exposure to Zn was found to confer significantly greater tolerance of the community to Pb. Prior exposure to Pb similarly conferred significantly greater tolerance of the community to Zn. Implications of the adaptive capacity of soil microbes to the development of critical threshold values for heavy metals in soil based on ecotoxicity assessments are discussed.     

Antimony (Sb) and arsenic (As) in Sb mining impacted paddy soil from Xikuangshan, China: differences in mechanisms controlling soil sequestration and uptake in rice

Foods produced on soils impacted by antimony (Sb) mining activities are a potential health risk due to plant uptake of the contaminant metalloids (Sb) and arsenic (As). Here we report for the first time the chemical speciation of Sb in soil and porewater of flooded paddy soil, impacted by active Sb mining, and its effect on uptake and speciation in rice plants (Oryza sativa L. cv Jiahua). Results are compared with behavior and uptake of As. Pot experiments were conducted under controlled conditions in a climate chamber over a period of 50 days. In pots without rice plants, flooding increased both the concentration of dissolved Sb (up to ca. 2000 μg L(-1)) and As (up to ca. 1500 μg L(-1)). When rice was present, Fe plaque developing on rice roots acted as a scavenger for both As and Sb, whereby the concentration of As, but not Sb, in porewater decreased substantially. Dissolved Sb in porewater, which occurred mainly as Sb(V), correlated with Ca, indicating a solubility governed by Ca antimonate. No significant differences in bioaccumulation factor and translocation factor between Sb and As were observed. Greater relative concentration of Sb(V) was found in rice shoots compared to rice root and porewater, indicating either a preferred uptake of Sb(V) or possibly an oxidation of Sb(III) to Sb(V) in shoots. Adding soil amendments (olivine, hematite) to the paddy soil had no effect on Sb and As concentrations in porewater.     

Uptake of metals during chelant-assisted phytoextraction with EDDS related to the solubilized metal concentration

The use of chelants to enhance phytoextraction is one method being tested to make phytoextraction efficient enough to be used as a remediation technique for heavy metal pollution in the field. We performed pot experiments with sunflowers in order to investigate the use of the biodegradable chelating agent SS-EDDS for this purpose. We used singly and combined contaminated soils (Cu, Zn) and multimetal contaminated field soils (Cu, Zn, Cd, Pb). EDDS (10 mmol kg(-10 soil) increased soil solution metals greatly for Cu (factor 840-4260) and Pb (factor 100-315), and to a lesser extent for Zn (factor 23-50). It was found that Zn (when present as the sole metal), Cu, and Pb uptake by sunflowers was increased by EDDS, butin multimetal contaminated soil Zn and Cd were not. EDDS was observed in the sunflower roots and shoots at concentrations equal to metal uptake. The different metal uptake in the various soils can be related to a linear relationship between Cu and Zn in soil solution in the presence of EDDS and plant uptake, indicating the great importance of measuring and reporting soil solution metal concentrations in phytoextraction studies.     

Remediation of methyl iodide in aqueous solution and soils amended with thiourea

Methyl iodide (MeI) is considered a very promising fumigant alternative to methyl bromide (MeBr) for controlling soil-borne pests. Because atmospheric emission of highly volatile fumigants contributes to air pollution, feasible strategies to reduce emissions are urgently needed. In this study, thiourea (a nitrification inhibitor) was shown to accelerate the degradation of MeI in soil and water. In aqueous solution, the reaction between MeI and thiourea was independent of pH, although the rate of MeI hydrolysis increased in alkaline solution. Substantial increases in the rate of MeI dissipation were observed in thiourea-amended soils. Transformation of MeI by thiourea in aqueous solution was by a single chemical reaction process, while MeI degradation in thiourea-amended soil apparently involved a catalytic mechanism. The electron delocalization between the thiourea molecule and the surfaces of soil particles is energetically favorable and would increase the nucleophilic reactivity of the thiono group toward MeI, resulting in an enhancement of the dissipation rate. The soil half-life for MeI was reduced from >300 h for unamended soils to only a few hours in soil or sand amended with thiourea at a 2:1 molar ratio (thiourea:MeI). The MeI transformation rate in thiourea-amended soil increased with increasing soil temperature and decreasing soil moisture. Therefore, spraying thiourea on the soil surface to form a "reactive surface barrier" may be an effective and innovative strategy for controlling fumigant emissions to the atmosphere and for improving environmental protection.     

Model demonstrating the potential for coupled nitrification denitrification in soil aggregates

A model of reactive, multi-species diffusion has been developed to describe N transformations in spherical soil aggregates, emphasizing the effects of irrigation with reclaimed wastewater. Oxygen demand for respiratory activity has been shown to promote the establishment of anaerobic conditions. Aggregate size and soil respiration rate were identified as the most significant parameters governing the existence and extent of the anaerobic volume in aggregates. The inclusion of kinetic models describing mineralization, nitrification, and denitrification facilitated the investigation of coupled nitrification/denitrification (CND), subject to O2 availability. N-transformations are shown to be affected by effluent-borne NH4+-N content, in addition to elevated BOD and pH levels. Their incremental contribution to O2 availability has been found to be secondary to respiratory activity. At the aggregate level, significant differences between apparent and gross rates of N-transformations were predicted (e.g., NH4+ oxidation and N2 formation), resulting from diffusive constraints due to aggregate size. With increasing anaerobic volume, the effective nitrification rate determined at the aggregates level decreases until its contribution to nitrification is negligible. It was found that the nitrification process was predominantly limited to aggregates <0.25 cm. Assuming that nitrification is the main source for NO3- formation, denitrification efficiency is predicted to peak in medium-sized aggregates, where aerobic and anaerobic conditions coexist, supporting CND. In effluent-irrigated soils, the predicted NO2- formation rate in small aggregates is enhanced when compared to freshwater-irrigated soils. The difference vanishes with increasing aggregate size as anaerobic NO2- consumption exceeds aerobic NO2- formation due to the coupling of nitrification and denitrification.     

Bioaccumulation of pharmaceuticals and other anthropogenic waste indicators in earthworms from agricultural soil amended with biosolid or swine manure

Analysis of earthworms offers potential for assessing the transfer of organic anthropogenic waste indicators (AWIs) derived from land-applied biosolid or manure to biota. Earthworms and soil samples were collected from three Midwest agricultural fields to measure the presence and potential for transfer of 77 AWIs from land-applied biosolids and livestock manure to earthworms. The sites consisted of a soybean field with no amendments of human or livestock waste (Site 1), a soybean field amended with biosolids from a municipal wastewater treatment plant (Site 2), and a cornfield amended with swine manure (Site 3). The biosolid applied to Site 2 contained a diverse composition of 28 AWls, reflecting the presence of human-use compounds. The swine manure contained 12 AWls, and was dominated by biogenic sterols. Soil and earthworm samples were collected in the spring (about30 days after soil amendment) and fall (140-155 days after soil amendment) at all field sites. Soils from Site 1 contained 21 AWIs and soil from Sites 2 and 3 contained 19 AWls. The AWI profiles at Sites 2 and 3 generally reflected the relative composition of AWls present in waste material applied. There were 20 AWls detected in earthworms from Site 1 (three compounds exceeding concentrations of 1000 microg/kg), 25 AWls in earthworms from Site 2 (seven compounds exceeding concentrations of 1000 microg/ kg), and 21 AWls in earthworms from Site 3 (five compounds exceeding concentrations of 1000 microg/kg). A number of compounds thatwere present in the earthworm tissue were at concentrations less than reporting levels in the corresponding soil samples. The AWIs detected in earthworm tissue from the three field sites included pharmaceuticals, synthetic fragrances, detergent metabolites, polycyclic aromatic hydrocarbons (PAHs), biogenic sterols, disinfectants, and pesticides, reflecting a wide range of physicochemical properties. For those contaminants detected in earthworm tissue and soil, bioaccumulation factors (BAF) ranged from 0.05 (galaxolide) to 27 (triclosan). This study documents that when AWls are present in source materials that are land applied, such as biosolids and swine manure, AWls can be transferred to earthworms.     

Persistence and biodegradation of monoethanolamine and 2-propanolamine at an abandoned industrial site

Soil and groundwater samples were collected at the site of a former chemical processing plant in areas impacted by accidental releases of MEA (monoethanolamine) and IPA (2-propanolamine or isopropanolamine). Although their use had ceased ca. 10 years before sample collection, soils collected at contamination sites had MEA concentrations ranging from ca. 400 to 3000 mg/kg and IPA concentrations from ca. 30 to 120 mg/kg. Even though alkanolamines are miscible in water, transport to groundwater was slow, apparently because they are present in soil as bound cations. Only one groundwater sample (near the most highly contaminated soil)from wells directly adjacentto and down-gradient from the contaminated soils had detectable MEA, and none had detectable IPA. However, ammonia was found in the soil samples collected in the MEA-contaminated areas (ca. 500-1400 mg/kg) and the groundwater (80-120 mg/L), as would be consistent with bacterial degradation of MEA to ammonia, followed by transport of ammonia into the groundwater. Counts for bacteria capable of using MEA or IPA as a sole carbon source were ca. 5 x 106 and 1 x 106 (respectively) per gram in uncontaminated site soil, but no such organisms were found in highly contaminated soils. Similarly, bacterial degradation of MEA in slurries of highly contaminated soils was slow, with ca. 8-20 days required for half of the initial concentrations of MEA to be degraded at 20 degrees C and 30-60 days at 10 degrees C. In contrast, bacterial degradation studies using uncontaminated site soils spiked with ca. 1300 mg/L either MEA or IPA showed very rapid degradation of both compounds,with more than 99% degradation occurring in less than 3 days with quantitative conversion to ammonia, followed by slower conversion to nitrite and nitrate. The results obtained in the site soils, the groundwater samples, and from the biodegradation studies demonstrate that MEA and IPA can persist for decades on soil at high (hundreds of mg/kg) concentrations without significant migration into groundwater, despite the fact that they are miscible in water. Since MEA and IPA exist primarily as cations at the pH of site soils, their persistence apparently results from strong binding to soil, as well as inhibition of natural bioremediation in highly contaminated field soils.     

Persistence of enterohemorrhagic Escherichia coli O157:H7 in soil and on leaf lettuce and parsley grown in fields treated with contaminated manure composts or irrigation water

Outbreaks of enterohemorrhagic Escherichia coli O157:H7 infections associated with lettuce and other leaf crops have occurred with increasing frequency in recent years. Contaminated manure and polluted irrigation water are probable vehicles for the pathogen in many outbreaks. In this study, the occurrence and persistence of E. coli O157:H7 in soil fertilized with contaminated poultry or bovine manure composts or treated with contaminated irrigation water and on lettuce and parsley grown on these soils under natural environmental conditions was determined. Twenty-five plots, each 1.8 by 4.6 m, were used for each crop, with five treatments (one without compost, three with each of the three composts, and one without compost but treated with contaminated water) and five replication plots for each treatment. Three different types of compost, PM-5 (poultry manure compost), 338 (dairy manure compost), and NVIRO-4 (alkaline-stabilized dairy manure compost), and irrigation water were inoculated with an avirulent strain of E. coli O157:H7. Pathogen concentrations were 10(7) CFU/g of compost and 10(5) CFU/ml of water. Contaminated compost was applied to soil in the field as a strip at 4.5 metric tons per hectare on the day before lettuce and parsley seedlings were transplanted in late October 2002. Contaminated irrigation water was applied only once on the plants as a treatment in five plots for each crop at the rate of 2 liters per plot 3 weeks after the seedlings were transplanted. E. coli O157:H7 persisted for 154 to 217 days in soils amended with contaminated composts and was detected on lettuce and parsley for up to 77 and 177 days, respectively, after seedlings were planted. Very little difference was observed in E. coli O157:H7 persistence based on compost type alone. E. coli O157:H7 persisted longer (by > 60 days) in soil covered with parsley plants than in soil from lettuce plots, which were bare after lettuce was harvested. In all cases, E. coli O157:H7 in soil, regardless of source or crop type, persisted for > 5 months after application of contaminated compost or irrigation water.     

Long-term aging of copper added to soils

Aging refers to the processes by which the mobility and bioavailability/toxicity of metals added to soil decline with time. Although long-term aging is a key process that needs to be considered in the risk assessment of metals in field soils, the long-term aging of Cu added to soils has not been studied in detail. In this study, the effects of aging on Cu isotopic exchangeability, total Cu in soil pore water, pore water free Cu2+ activity, and "available" Cu measured by the technique of diffusive gradient in thin film (DGT-Cu) were investigated in 19 European soils at two total Cu concentrations shown to inhibit plant (tomato) growth by 10 and 90%. After addition of Cu, the soils were leached, incubated outdoors, and sampled regularly over a 2-year period. The results showed that when water soluble Cu was added to soils, concentrations of Cu determined by each of the techniques tended to decrease rapidly initially, followed by further decreases at slow rates. Soil pH was a vital factor affecting the aging rate of Cu added to soils. The relatively low solubility products and low isotopic exchangeabilities of Cu in calcareous soils immediately after addition of soluble Cu2+ suggested Cu2+ probably precipitated in these soils as Cu2(OH)2CO3 (malachite) and Cu(OH)2. Isotopic dilution was found to be a robust technique for measuring rates of long-term aging reactions. A semi-mechanistic model was developed to describe the rate and extent of Cu aging across soils as affected by soil pH and other physicochemical parameters. Although not measured directly, it is inferred from soil physicochemical controls on Cu aging that processes of precipitation/nucleation of Cu in soils and hydrolysis of Cu2+ followed by a diffusion process controlled the decrease in Cu availability with time. The model was validated by testing it against field soils with different contamination histories and was found to successfully predict the isotopic exchangeability of Cu added to soils based on two parameters: soil pH and time.     

Breakdown of WL 9385, an azido triazine herbicide, in soils and on wheat

The breakdown of the herbicide WL 9385 (2-azido-4-ethylamino-6-t-butylamino-l, 3, 5-triazine) in soils and in spring wheat has been studied in the laboratory by radio-isotope techniques. In soils the major long-term breakdown product was formed by the reduction of the azido group to an amino group together with smaller amounts of a subsequent de-ethylation reaction product. On the foliage of spring wheat the reduction reaction also occurred and de-ethylation of the reduction product was also evident, but with some de-ethylation of WL 9385 itself. Spring wheat grown in soils treated with the herbicide at 2 kg/ha contained residues of 2.2 ppm (as equivalent ppm of WL 9385) of metabolites in the seed head and 7.4 ppm in the rest of the plant above ground at harvest at 65 days from treatment. Residues of ¹⁴C-compounds could not be detected in the seed head of wheat which had received a foliar application of 10 ppm of ¹⁴C-WL 9385 at 100 days before harvest and residues in the rest of the plant above ground were only 0.16 ppm. The breakdown products are not of higher acute toxicity to rats than the parent compound and the major soil breakdown products are not herbicidal.