Reducing 1,3-dichloropropene emissions from soil columns amended with thiourea

Soil fumigants are becoming an important source of volatile organic compounds (VOCs) in air, especially in some agricultural areas. In this study, we used thiourea to construct a reactive surface barrier (RSB) at the soil surface for reducing 1,3-dichloropropene (1,3-D) volatilization. The agrochemical thiourea could rapidly transform volatile 1,3-D to nonvolatile products via an SN2 nucleophilic substitution reaction. A catalytic mechanism in thiourea-amended soil facilitated the conversion process. A packed soil column system was employed to investigate the emissions and distribution of 1,3-D and optimize the original fumigant emission-reduction strategy. Volatilization of 1,3-D from the soil surface was significantly reduced in columns amended with a thiourea RSB compared with that of bare soil. Volatilization flux and cumulative emissions decreased with increasing thiourea application rate and increasing fumigation depth in packed soil columns. Surface amendment with the RSB did not affect the subsurface distribution of 1,3-D in the soil profile. Combined application of a thiourea RSB and plastic tarps had a synergetic effect in emission control and could eliminate the relatively high fumigant flux that occurs upon tarp disruption. Therefore, this reduced-risk practice was very effective in reducing atmospheric emissions of VOCs from soil treatment with halogenated fumigants.     

Thiosulfate and manure amendment with water application and tarp on 1,3-dichloropropene emission reductions

Reducing fumigant emissions is required for minimizing bystander risk and environmental impact. Effective and economic field management methods including commonly used surface sealing technique and soil amendments are needed for achieving emission reductions. This research determined the effectiveness of ammonium thiosulfate (ATS) and composted manure amendments to surface soil in combination with water application or high density polyethylene (HDPE) tarp on reducing emissions of 1,3-D from soil columns. Surface treatments included an untreated control, water seal (single water application at time of fumigant injection), ATS amendments at 1:1 and 2:1 molar ratio of ATS:fumigant, composted steer manure at 3.5 kg m(-2), and HDPE tarp over 1:1 ATS or the manure amendment. Cumulative 1,3-D emission loss over two weeks was greatest for the control (52% of applied). The HDPE tarp over ATS and manure treatments had the lowest 1,3-D emissions at 24 and 16%, respectively. Treatments with ATS or manure alone reduced 1,3-D emissions (29-39%) more effectively than water seal (43%) and further benefit was gained with the addition of HDPE tarp. Amendment of surface soil with organic materials shows greater potential in minimizing fumigant emissions than with chemicals with the need for a better understanding of the organic-fumigant reaction mechanism.     

Effect of surface tarp on emissions and distribution of drip-applied fumigants

Soil fumigants are used to control a wide variety of soil-borne pests in high-cash-value crops. Application of soil fumigants through drip irrigation systems is receiving increasing attention as a method to improve the uniformity of fumigant application. Little information is available on the emissions and soil distribution of fumigants following subsurface drip application, or the effect of plastic tarp on fumigant emissions in these systems. In these experiments, the fumigant compounds 1,3-dichloropropene (1,3-D), Vapam (a methyl isothiocyanate (MITC) precursor), and propargyl bromide (PrBr) were applied to soil beds via drip irrigation at 15 cm depth. Beds were tarped with either standard 1-mil high-density polyethylene (HDPE) or a virtually impermeable film (VIF), leaving the furrows bare. Cumulative emissions of 1,3-D, MITC, and PrBr in these tarped bedded systems was very low, amounting to <10% of the applied mass. These experiments were conducted in the winter months, with average air temperatures of 12-15 degrees C. Cumulative emissions of MITC and 1,3-D from a sandy loam field soil were decreased by > or =80% by tarping the bed with VIF rather than HDPE. A large fraction of the 1,3-D and PrBr flux was from the untarped furrows in VIF-tarped plots, indicating that inhibiting volatilization from the furrow will be important in further reducing emissions in these systems. Monitoring the fumigant distribution in soil indicated that tarping the bed with VIF resulted in a more effective containment of fumigant vapors compared to use of a HDPE tarp.     

Formation and extraction of persistent fumigant residues in soils

Fumigants are commonly thought to be short-lived in soil, but residues have been found in soils years following application. In this study, formation and extraction of persistent soil fumigant residues were investigated. Fumigants 1,3-dichloropropene (1,3-D), chloropicrin (CP), and methyl isothiocyanate (MITC) were spiked into Arlington, Glenelg, and Hagerstown soils and incubated for 30 d under controlled conditions. The incubated soils were evaporated for 20 h prior to extraction with a variety of organic solvents at different temperatures. Extraction with acetonitrile in sealed vials at 80 degrees C for 24 h was the most efficient method to recover persistent soil fumigant residues. At application rates of 1000-1700 mg (kg of soil)(-1), persistent residues of 1,3-D, CP, and MITC in the three soils ranged from 5 to 67 mg kg(-1). The residue content increased with application rate, correlated positively with soil silt content, decreased dramatically as indigenous organic matter (OM) was removed, and changed little with external OM addition. Adsorption to clay surfaces was not important in fumigant retention, while pulverization of soil aggregates significantly decreased persistent fumigant residues. The results suggest that persistent fumigant residues are retained in soil intra-aggregate micropores resulting from binding clay flocs and silt particles by humic substances.     

Leaching potential of persistent soil fumigant residues

Persistent fumigant residues in soil resulting from agricultural pest-control practices may be released into water and leached to groundwater. In this study, the leaching potential of persistent soil fumigant residues was evaluated, and the effect of dissolved organic matter (DOM) and ammonium thiosulfate (ATS) amendment was investigated. A silt loam soil was incubated separately with the fumigants 1,3-dichloropropene (1,3-D), chloropicrin (CP), and methyl isothiocyanate (MITC) at 240-990 mg kg(-1) for 35 d, followed by 48 h of evaporation. The soil was packed into stainless steel columns (1.4 cm x 10 cm) and leached with water, 5 mM ATS, and DOM solution (DOC 250 mg L(-1)) by gravity. Residues of 1,3-D, CP, and MITC in the evaporated soil were 5.61, 11.38, and 1.83 mg kg(-1), respectively. Concentrations of 1,3-D, CP, and MITC in column effluents ranged from 0.05 to 0.73, 0.16 to 0.81, and 0.05 to 0.27 mg L(-1), respectively, when the soil was leached with 10 pore volumes of water. DOM did not promote the leaching of persistent fumigant residues, and ATS remarkably reduced the amount of 1,3-D and CP yet notably increased MITC recovered in the effluents. The results suggest that the leaching of persistent fumigant residues through soil to water is significant, and movement of fumigants in soil is not facilitated by DOM. Amending soil with ATS through irrigation is an effective method to remove persistent residues of halogenated fumigants. To reduce groundwater pollution risks posed by fumigation, persistent soil fumigant residues have to be considered.     

Temporal and spatial water use on irrigated and nonirrigated pasture-based dairy farms

Robust information for water use on pasture-based dairy farms is critical to farmers' attempts to use water more efficiently and the improved allocation of freshwater resources to dairy farmers. To quantify the water requirements of dairy farms across regions in a practicable manner, it will be necessary to develop predictive models. The objectives of this study were to compare water use on a group of irrigated and nonirrigated farms, validate existing water use models using the data measured on the group of nonirrigated farms, and modify the model so that it can be used to predict water use on irrigated dairy farms. Water use data were collected on a group of irrigated dairy farms located in the Canterbury, New Zealand, region with the largest area under irrigation. The nonirrigated farms were located in the Manawatu region. The amount of water used for irrigation was almost 52-fold greater than the amount of all other forms of water use combined. There were large differences in measured milking parlor water use, stock drinking water, and leakage rates between the irrigated and nonirrigated farms. As expected, stock drinking water was lower on irrigated dairy farms. Irrigation lowers the dry matter percentage of pasture, ensuring that the amount of water ingested from pasture remains high throughout the year, thereby reducing the demand for drinking water. Leakage rates were different between the 2 groups of farms; 47% of stock drinking water was lost as leakage on nonirrigated farms, whereas leakage on the irrigated farms equated to only 13% of stock drinking water. These differences in leakage were thought to be related to regional differences rather than differences in irrigated versus nonirrigated farms. Existing models developed to predict milking parlor, corrected stock drinking water, and total water use on nonirrigated pasture-based dairy farms in a previous related study were tested on the data measured in the present research. As expected, these models performed well for nonirrigated dairy farms but provided poor predictive power for irrigated farms. Partial least squares regression models were developed specifically to simulate corrected stock drinking water, milking parlor water, and total water use on irrigated dairy farms.     

Soil chamber method for determination of drip-applied fumigant behavior in bed-furrow agriculture: application to chloropicrin

To overcome the environmental impacts of soil fumigant use, emission reduction strategies such as tarping can be adopted. There is a need to experimentally quantify the effectiveness of such strategies, preferably in a low-cost manner. We report the design and initial testing of a laboratory soil chamber approach for quantifying the soil distribution and emissions of fumigants from bed-furrow agricultural systems. As far as possible, field conditions (e.g., soil type, bulk density, moisture content temperature) were maintained in the experiments. In studying the drip application of chloropicrin using this system, very good data reproducibility was observed between replicates, allowing confidence in the experimental design. For control chambers, high emissions, around 60% (of the total added), were observed due to the near-surface (5 cm depth) application. When the soil beds were tarped using high-density polyethylene (HDPE) or semi-impermeable film (SIF), emissions were reduced to around 40% due to an accumulation of chloropicrin below the tarp. The approach offers an inexpensive potential alternative to studying fumigant emissions from bed-furrow systems in the field and suggests that less permeable tarps would be required to drastically reduce chloropicrin emissions.     

Effect of application variables on emissions and distribution of fumigants applied via subsurface drip irrigation

Soil fumigation is useful for controlling soil-borne pests and diseases in high-cash-value crops. Fumigants are highly volatile, and approaches to reduce atmospheric emissions are required to protect human and environmental health. Application of fumigants through drip irrigation has been proposed as a means to decrease fumigant emissions, improve fumigant distribution in soil, and minimize worker exposure. These experiments were conducted to investigate the effect of the configuration of the drip system on the volatilization and distribution of the fumigants 1,3-dichloropropene (1,3-D), propargyl bromide (PrBr), and methyl isothiocyanate (MITC) in bedded systems. Results indicated that changing the drip emitter spacing and using multiple drip lines in each bed had little effect on the emissions and distribution of any fumigant. Increasing the depth of application from 15 to 30 cm reduced volatilization of MITC by approximately 20 to >90%; emissions were reduced due to a decrease in the flux from the bed top, and deeper injection did not change the amount of fumigant volatilized from the bed side slope and furrow. Increasing the application depth resulted in a slight decrease in the rate of fumigant dissipation in soil, indicating the potential for some improvement in pest-control efficacy with deeper application.     

Identification of volatile/semivolatile products derived from chemical remediation of cis-1,3-dichloropropene by thiosulfate

The prevalent use of soil fumigants has resulted in air pollution in some agricultural regions. Our previous research showed that application of thiosulfate fertilizers at the soil surface may offer an effective and economical approach to reduce the emission of halogenated fumigants via a chemical remediation process. In this fumigant emission-reduction strategy, volatile 1,3-dichloropropene (1,3-D) reacts with thiosulfate to generate a nonvolatile Bunte salt (thiosulfate derivative of 1,3-D). However, the decomposition of the Bunte salt may be associated with the production of perceptible odors. This study investigated the stability of this reaction product in different environmental media. Hydrolysis experiments demonstrated that the thiosulfate derivative was relatively stable in neutral and moderately acidic aqueous solutions. In contrast, the thiosulfate derivative was readily converted to a dialkyl disulfide via a base hydrolysis process in pH 10 buffer solution. In a strongly acidic solution, a mercaptan and a dialkyl disulfide compound were detected as two primary hydrolysis products. In soil, this initial reaction product underwent a series of biotic conversions to generate several volatile or semivolatile organic sulfur compounds. The formation and distribution of four volatile/semivolatile products in the air and soil were detected in different soils treated with the thiosulfate derivative of 1,3-D. This study indicated that odors occurring in soil treated with halogenated fumigants and thiosulfate fertilizers might arise from the generation and release of these and other volatile/semivolatile organic sulfur products. The environmental fate and effects of such volatile/semivolatile sulfur compounds should be considered in the application of sulfur-containing fertilizers in fumigated fields.     

Mitigating 1,3-dichloropropene, chloropicrin, and methyl iodide emissions from fumigated soil with reactive film

Implicated as a stratospheric ozone-depleting compound, methyl bromide (MeBr) is being phased out despite being considered to be the most effective soil fumigant. Its alternatives, i.e., 1,3-dichloropropene (1,3-D, which includes cis and trans isomers), chloropicrin (CP), and methyl iodide (MeI), have been widely used. High emissions of MeI from fumigated soil likely put farm workers and other bystanders at risk of adverse health effects. In this study, two types of constructed reactive film were tested for their ability to mitigate emissions of 1,3-D, CP, and MeI using laboratory permeability cells. Before activation, these films act as a physical barrier to trap fumigants leaving soil. After activation of the reactive layer containing ammonium thiosulfate solution, the films also act as a sink for the fumigants. Over 97% of trans-1,3-D and 99% of the cis-1,3-D, CP and MeI were depleted when they passed into the reactive film. Half-lives (t(1/2)) of cis-, trans-1,3-D, CP and MeI under activated reactive film were 1.2, 1.4, 1.6, and 2.0 h respectively at 40 °C.     

Effect of environmental conditions on the permeability of high density polyethylene film to fumigant vapors

Soil fumigation in greenhouses or agricultural fields often includes tarping the soil surface with polyethylene (PE) films to contain the fumigant in the soil and reduce emissions to the atmosphere. Previous research has demonstrated that PE films are permeable to methyl bromide and other fumigant compounds. In these experiments, the effect of temperature, fumigant mixtures, condensed water, and field aging on the permeability of high-density polyethylene (HDPE) was determined. Mass transfer coefficients (h, a measure of permeability) of the fumigants methyl bromide, 1,3-dichloropropene, propargyl bromide, and chloropicrin across HDPE films were determined. In these studies, temperature and HDPE film type had the largest impact on the h of fumigant compounds across HDPE films. Other factors investigated, including fumigant mixtures, condensed water on the film, and field aging of UV-stabilized film, did not have a significant impact on h. The results of these experiments suggest that the permeability of an intact piece of an agricultural film will increase with increasing temperature but is relatively constant despite changes in other environmental conditions.     

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.     

EFFECT OF A DEFICIT IRRIGATION REGIME ON THE QUALITY OF WINES MADE FROM WHITE GRAPES (VITIS VINIFERA L.) GROWN IN SEMIARID AREAS

ABSTRACT

The dependence of wine quality on the irrigation management strategies in Vitis vinifera L. was tested from 1999 to 2002. A drip‐irrigation experiment was performed on white grapes of the cultivars Baladí, Airén, Montepila, Muscat Blanc à Petits Grains and Pedro Ximénez, grafted and vineyard‐planted in 1995 in Cabra (Cordoba, Spain). Treatments consisted of a nonirrigated control and an experimental deficit irrigation, in which water was applied from fruit set until near harvest. A total of 19 analytical parameters were measured, including alcohols, total phenol content and optical density as well as ethanol, pH, total acidity and dry extract. Wines were evaluated for their visual characteristics, aroma, taste and finish. The irrigation treatment contributed to a higher dry extract, and an increase in malic acid and potassium in wines. There was a decrease in pH, isobutanol and isoamyl alcohols with increasing water application. Sensory evaluation ranked irrigated over nonirrigated wines with the only exception of the wines of Muscat Blanc à Petits Grains. The main defects of nonirrigated wines were attributed to visual characteristics and poorer taste quality.

PRACTICAL APPLICATIONS

Proper irrigation management, i.e., optimizing both the timing and the amount of water supplied, plays a significant role in wine quality and is especially important in arid and semiarid areas. The aim of this study was to ascertain the effect of irrigation in wine quality. In this study, irrigation was applied only during periods in which water stress might affect production and harvest quality. The chemical results ranked irrigated over nonirrigated wines and Muscat Blanc à Petits Grains over other cultivars, regarding their quality. Sensory evaluation ranked irrigated over nonirrigated wines with the only exception of the wines of Muscat Blanc à Petits Grains. Therefore, deficit irrigation during berry development and ripening appears to be a promising technique for the production of quality young wines in semiarid achieving a compromise between aroma and taste quality.     

造纸废水污灌对土壤性质及脲酶活性的影响

通过大田试验和实验室盆栽实验,研究了造纸废水污灌对土壤理化性质、呼吸强度和脲酶活性的影响及其时间的动态变化规律。结果表明,造纸废水长期污灌后,土壤有机质含量表现为少量增加,而盐碱性增强。污水灌溉早期会刺激土壤呼吸作用,浓度越大,作用越明显;后期逐渐恢复,25 d后恢复至对照水平。对土壤脲酶,则表现为先抑制、后恢复。     

Interaction of methyl bromide with soil

Because methyl bromide (CH3Br) is a widely used agricultural fumigant for soil disinfection, it is important to know the chemical behavior and fate of CH3Br as a result of its use for soil treatment. A solid-state 13C NMR study of 13CH3Br-treated soil and soil-component samples shows that methylation of soil organic matter may be the major pathway for degradation of CH3Br in soils. Adsorption of CH3Br on a dried clay like Ca-montmorillonite or kaolinite does not contribute directly to the degradation of CH3Br. The results are interpreted in terms of the chemical structures of separated soil fractions and the nature of the separation procedure.     

Effects of microbially mediated redox conditions on PAH-soil interactions

The impacts of microbially mediated redox conditions on the bioavailability of persistent polycyclic aromatic hydrocarbons (PAHs) in soils and sediments have received little study, despite the fact that most water-saturated soils and sediments spend a significant portion of the time under reduced conditions. To address this need an uncontaminated surface soil was incubated under various redox conditions (aerobic, nitrate-reducing, sulfate-reducing, and methanogenic). Depending on redox conditions, different quantities of fulvic and humic acids were liberated as dissolved organic matter (DOM) from the soil during incubation. The DOM released under highly reduced conditions was more nonpolar, aromatic, and polydisperse, of higher molecular weight, and had a higher sorption capacity for pyrene compared to that obtained from relatively oxic incubations. The soil-phase organic matter incubated under reduced conditions also became relatively more aromatic, containing nonpolar organic molecules of lower oxygen contents and exhibiting higher capacity and more nonlinear and hysteric sorption/desorption behavior for pyrene. These observations support the hypothesis that reduced environments established by indigenous soil microbes alter soil organic matter in a matter similar to diagenetic processes. Such humification-like alteration occurred principally in relatively more labile fractions of soil organic matter. These findings are important for assessing the ultimate fate and exposure risk of hydrophobic organic contaminants in soils and sediments where living microorganisms play a significant role in formation and evolution of soil/sediment organic matter.     

等碳量添加不同有机物料对土壤有机碳组分及土壤呼吸的影响

为探明不同有机物料对土壤有机碳组分和呼吸速率的影响,研究了等碳量添加生物炭、秸秆、生物炭+秸秆条件下烤烟生长过程中土壤总有机碳（TOC）、易氧化有机碳（ROC）、可溶性有机碳（DOC）、微生物量碳（MBC）含量及土壤呼吸速率的动态变化,分析了土壤各有机碳组分之间及其与土壤呼吸速率的关系。研究结果显示,与单施化肥相比,等碳量添加有机物料后土壤各有机碳组分含量以及土壤呼吸速率均显著提高;添加有机物料的3个处理中,单施生物炭处理土壤TOC含量最高,CO₂排放量最低;单施秸秆处理土壤活性有机碳（AOC）占TOC的比例及CO₂排放量最高,但TOC含量最低;生物炭+秸秆处理土壤TOC含量显著高于添加秸秆处理,AOC含量显著高于单施生物炭处理,且CO₂排放量显著低于单施秸秆处理。土壤ROC、DOC、MBC之间关系密切,三者与土壤呼吸速率均呈显著正相关。由此可见,等碳量添加有机物料条件下,生物炭有利于土壤有机碳的固存,可减少CO₂的排放,但短期内对提高土壤AOC的效果不如秸秆直接还田明显,而秸秆直接还田对土壤AOC含量的提升效果最好,但会增加CO₂的排放,两者配施既提高了土壤AOC的含量,又减少了CO₂的排放。      

Hexavalent uranium diffusion into soils from concentrated acidic and alkaline solutions

Uranium contamination of soils and sediments often originates from acidic or alkaline waste sources, with diffusion being a major transport mechanism. Measurements of U(VI) diffusion from initially pH 2 and pH 11 solutions into a slightly alkaline Altamont soil and a neutral Oak Ridge soil were obtained through monitoring uptake from boundary reservoirs and from U concentration profiles within soil columns. The soils provided pH buffering, resulting in diffusion at nearly constant pH. Micro X-ray absorption near edge structure spectra confirmed that U remained in U(VI) forms in all soils. Time trends of U(VI) depletion from reservoirs and U(VI) concentration profiles within soil columns yielded Kdvalues consistent with those determined in batch tests at similar concentrations (approximately 1 mM) and much lower than values for sorption at much lower concentrations (nM to microM). These results show that U(VI) transport at high concentrations can be relatively fast at non-neutral pH, with negligible surface diffusion, because of weak sorption.     

Linking phosphorus sequestration to carbon humification in wetland soils by 31P and 13C NMR spectroscopy

Phosphorus sequestration in wetland soils is a prerequisite for long-term maintenance of water quality in downstream aquatic systems, but can be compromised if phosphorus is released following changes in nutrient status or hydrological regimen. The association of phosphorus with relatively refractory natural organic matter (e.g., humic substances) might protect soil phosphorus from such changes. Here we used hydrofluoric acid (HF) pretreatment to remove phosphorus associated with metals or anionic sorption sites, allowing us to isolate a pool of phosphorus associated with the soil organic fraction. Solution (31)P and solid state (13)C NMR spectra for wetland soils were acquired before and after hydrofluoric acid pretreatment to assess quantitatively and qualitatively the changes in phosphorus and carbon functional groups. Organic phosphorus was largely unaffected by HF treatment in soils dominated by refractory alkyl and aromatic carbon groups, indicating association of organic phosphorus with stable, humified soil organic matter. Conversely, a considerable decrease in organic phosphorus following HF pretreatment was detected in soils where O-alkyl groups represented the major fraction of the soil carbon. These correlations suggest that HF treatment can be used as a method to distinguish phosphorus fractions that are bound to the inorganic soil components from those fractions that are stabilized by incorporation into soil organic matter.     

恩施烟区土壤养分状况调查

通过对恩施烟区272个土壤样品所进行的测定,评价了植烟土壤养分状况。结果表明,全州90%以上被调查土壤适宜种植烟草,50%的样品有机质含量较为适宜,近35%的样品有机质含量偏高,60%土壤全氮适宜。近60%的土壤碱解氮偏高,77.65%的土壤速效磷含量适中且部分偏高,但仍然有近23%的土壤速效磷含量偏低或缺乏;60%以上被调查土壤平均速效钾含量偏低,且区域间差异较大。土壤普遍缺镁,72.06%的被调查土壤交换性镁含量低于0.4 cmol/kg,变异系数为84.51%;30.51%的被调查土壤缺硼,56.99%的土壤存在缺硼风险;全州范围内大多数土壤有效锌含量适宜,部分偏高,但含量差异大,变异系数高。