Modeling pesticide volatilization from turf

Pesticide volatilization models are typically based on equilibrium partitioning of the chemical into solid, liquid, and gaseous phases in the soil environment. In turf systems direct vaporization from vegetation surfaces is a more likely source, and it is difficult to apply equilibrium methods to plant material due to the uncertainties of solid-liquid-gas partitioning. An alternative approach is to assume that pesticide volatilization is governed by the same processes that affect water evaporation. A model was developed in which evapotranspiration values, as determined by the Penman equation, were adjusted to chemical vaporization using ratios of water and chemical saturated vapor pressures and latent heats of vaporization. The model also assumes first-order degradation of pesticide on turf vegetation over time. The model was tested by comparisons of predictions with measurements of volatilization for eight pesticides measured during 3 to 7 d in 11 field experiments. Measured volatilization fluxes ranged from 0.1 to 22% of applied chemical. Pesticides were divided into two groups based on saturated vapor pressures and organic C partition coefficients. One pesticide was selected from each group to calibrate the model's volatilization constant for the group, and the remaining pesticides were used for model testing. Testing results indicated that the model provides relatively conservative estimates of pesticide volatilization. Predicted mean losses exceeded observations by 20%, and the model explained 67% of the observed variation in volatilization fluxes. The model was most accurate for those chemicals that exhibited the largest volatilization losses.     

Volatilization and degradation of soil-applied dimethylselenide

Dimethylselenide (DMSe) is a highly volatile gas that is produced by indigenous microorganisms in seleniferous soils and sediments; however, little is known about the soil conditions that affect the persistence of DMSe and its transport to the atmosphere. In this study we investigated the effect of moisture content, temperature, and organic amendments on the degradation of soil-applied DMSe. The degradation of DMSe was entirely a result of biological mechanisms, but changes in temperature (20-40 degrees C) and soil moisture content (30-70% of the maximum water holding capacity) had little influence on the degradation rate. In contrast, amending soil with either 1% casein or gluten (by weight) had an inhibitory effect on the degradation of DMSe. After 18 d, 2.1 times more DMSe was present in the casein-amended soil and 2.6 times more DMSe was present in the gluten-amended soil. The transport of DMSe in packed soil columns was also investigated. Increasing the depth to soil surface was found to significantly decrease the amount of DMSe transported to the air. After 6 d, 57% of DMSe injected 10 cm below the soil surface was volatilized. At an injection depth of 20 cm the cumulative emissions were reduced by 38% and at 30 cm the cumulative emissions were reduced by 51%. In columns containing 1% casein or gluten in the top 5 cm of soil the cumulative loss of DMSe was about 9% higher than in unamended soil. Increasing our understanding of the soil conditions that influence the gaseous diffusion of DMSe should help in determining the feasibility of using Se volatilization as a remediation technique.     

Partitioning and persistence of trichlorfon and chlorpyrifos in a creeping bentgrass putting green

Golf course putting greens typically receive high pesticide applications to meet high quality demands. Research on pesticide fate in turf ecosystems is important to better understand the potential impact of pesticide use on the environment and human health. This research was conducted to evaluate the environmental fate of two commonly used insecticides--trichlorfon (dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate) and chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate)--in a creeping bentgrass (Agrostis palustris Huds.) putting green under customary field management practices at the University of California-Riverside Turf Research Facility during 1996 and 1997. The two insecticides were chosen because of their difference in water solubility, persistence, adsorption, and vapor pressure. Volatilization, clipping removal, and soil residues of the insecticides were quantified and leaching was monitored using lysimeters installed in putting green plots. Results showed trichlorfon volatilization, clipping removal, and leaching loss was insignificant (in the range of 0.0001-0.06% of applied mass) both in 1996 and 1997. No significant difference in clipping removal of trichlorfon and chlorpyrifos was observed in both years (0.06 and 0.05% of applied mass for trichlorfon and 0.15 and 0.19% of applied mass for chlorpyrifos, respectively, in 1996 and 1997), but significantly lower cumulative leaching and lower soil concentration was observed in 1997 than in 1996. Volatilization loss of chlorpyrifos was not significantly different between 1996 (2.05%) and 1997 (2.71%). Volatilization loss of trichlorfon in 1996 (0.01%) was significantly higher than in 1997 (0.008%). This study demonstrated the fraction of applied insecticides leaving the turf putting greens was minimal.     

Fate of diuron and linuron in a field lysimeter experiment

The environmental fate of herbicides can be studied at different levels: in the lab with disturbed or undisturbed soil columns or in the field with suction cup lysimeters or soil enclosure lysimeters. A field lysimeter experiment with 10 soil enclosures was performed to evaluate the mass balance in different environmental compartments of the phenylurea herbicides diuron [3-(3,4-diclorophenyl)-1,1-dimethyl-urea] and linuron [3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea]. After application on the agricultural soil, the herbicides were searched for in soil, pore water, and air samples. Soil and water samples were collected at different depths of the soil profile and analyzed to determine residual concentrations of both the parent compounds and of their main transformation products, to verify their persistence and their leaching capacity. Air volatilization was calculated using the theoretical profile shape method. The herbicides were detected only in the surface layer (0-10 cm) of soil. In this layer, diuron was reduced to 50% of its initial concentration at the end of the experiment, while linuron was still 70% present after 245 d. The main metabolites detected were DCPMU [3-(3,4-dichlorophenyl)-1-methylurea] and DCA (3,4-dichloroaniline). In soil pore water, diuron and linuron were detected at depths of 20 and 40 cm, although in very low concentrations. Therefore the leaching of these herbicides was quite low in this experiment. Moreover, volatilization losses were inconsequential. The calculated total mass balance showed a high persistence of linuron and diuron in the soil, a low mobility in soil pore water (less than 0.5% in leachate water), and a negligible volatilization effect. The application of the Pesticide Leaching Model (PELMO) showed similar low mobility of the chemicals in soil and water, but overestimated their volatilization and their degradation to the metabolite DCPMU. In conclusion, the use of soil enclosure lysimeters proved to be a good experimental design for studying mobility and transport processes of herbicides in field conditions.     

Trichloroethylene (TCE) removal in a single pulse suspension bioreactor

This work describes TCE biotic removal in a single-pulse bioreactor under aerobic conditions. Activated sludge from a wastewater-treatment plant was used for inoculation of the cultivator. The experiment focused on a more detailed verification of microbial composition of mixed heterotrophic culture during pulsed phenol dosage. Attention was given to suppressing eucaryotic organisms, particularly yeasts and fungi, by the addition of cycloheximide. The TCE-removal capacity of the heterotrophic culture, described by kinetic tests, was dependent on pulsed phenol injection and on cyclic addition of phenol and TCE. Maximum TCE degradation was determined in a batch test. It was found that the addition of cycloheximide (an antibiotic against propagation and growth of fungi and yeast) increased the TCE degradation activity of the mixed microbial suspension. A certain residual amount of TCE remained in some of the experiments.     

Loss pathways of N-nitrosodimethylamine (NDMA) in turfgrass soils

N-nitrosodimethylamine (NDMA) is a potent carcinogen that is often present in municipal wastewater effluents. In a previous field study, it was observed that NDMA did not leach through turfgrass soils following 4 mo of intensive irrigation with NDMA-containing wastewater effluent. To better understand the loss pathways for NDMA in landscape irrigation systems, a mass balance approach was employed using in situ lysimeters treated with 14C-NDMA. When the lysimeters were subjected to irrigation and field conditions after NDMA application, very rapid dissipation of NDMA was observed for both types of soil used in the field plots. After only 4 h, total 14C activity in the lysimeters decreased to 19.1 to 26.1% of the applied amount, and less than 1% of the activity was detected below the 20-cm depth. Analysis of plant materials showed that less than 3% of the applied 14C was incorporated into the plants, suggesting only a minor role for plant uptake in removing NDMA from the vegetated soils. The rapid dissipation and limited downward movement of NDMA in the in situ lysimeters was consistent with the negligible leaching observed in the field study, and suggests volatilization as the only significant loss pathway. This conclusion was further corroborated by rapid NDMA volatilization found from water or a thin layer of soil under laboratory conditions. In a laboratory incubation experiment, prolonged wastewater irrigation did not result in enhanced NDMA degradation in the soil. Therefore, although NDMA may be present at relatively high levels in treated wastewater, gaseous diffusion and volatilization in unsaturated soils may effectively impede significant leaching of NDMA, minimizing the potential for ground water contamination from irrigation with treated wastewater.     

Hycrest crested wheatgrass accelerates the degradation of pentachlorophenol in soil

We investigated the effects of vegetation on the fate of pentachlorophenol (PCP) in soil using a novel high-flow sealed test system. Pentachlorophenol has been widely used as a wood preservative, and this highly toxic biocide contaminates soil and ground water at many sites. Although plants are known to accelerate the rates of degradation of certain soil contaminants, this approach has not been thoroughly investigated for PCP. The fate of [14C]PCP, added to soil at a concentration of 100 mg/kg, was compared in three unplanted and three planted systems. The plant used was Hycrest, a perennial, drought-tolerant cultivar of crested wheatgrass [Agropyron desertorum (Fischer ex Link) Schultes]. The flow-through test system allowed us to maintain a budget for 14C-label as well as monitor mineralization (breakdown to 14CO2) and volatilization of the test compound in a 155-d trial. In the unplanted systems, an average of 88% of the total radiolabel remained in the soil and leachate and only 6% was mineralized. In the planted system, 33% of the radiolabel remained in the soil plus leachate, 22% was mineralized, and 36% was associated with plant tissue (21% with the root fraction and 15% with shoots). Mineralization rates were 23.1 mg PCP mineralized kg-1 soil in 20 wk in the planted system, and for the unplanted system 6.6 mg PCP kg-1 soil for the same time period. Similar amounts of volatile organic material were generated in the two systems (1.5%). Results indicated that establishing crested wheatgrass on PCP-contaminated surface soils may accelerate the removal of the contaminant.     

A dynamic two-dimensional system for measuring volatile organic compound volatilization and movement in soils

There is an important need to develop instrumentation that allows better understanding of atmospheric emission of toxic volatile compounds associated with soil management. For this purpose, chemical movement and distribution in the soil profile should be simultaneously monitored with its volatilization. A two-dimensional rectangular soil column was constructed and a dynamic sequential volatilization flux chamber was attached to the top of the column. The flux chamber was connected through a manifold valve to a gas chromatograph (GC) for real-time concentration measurement. Gas distribution in the soil profile was sampled with gas-tight syringes at selected times and analyzed with a GC. A pressure transducer was connected to a scanivalve to automatically measure the pressure distribution in the gas phase of the soil profile. The system application was demonstrated by packing the column with a sandy loam in a symmetrical bed-furrow system. A 5-h furrow irrigation was started 24 h after the injection of a soil fumigant, propargyl bromide (3-bromo-1-propyne; 3BP). The experience showed the importance of measuring lateral volatilization variability, pressure distribution in the gas phase, chemical distribution between the different phases (liquid, gas, and sorbed), and the effect of irrigation on the volatilization. Gas movement, volatilization, water infiltration, and distribution of degradation product (Br-) were symmetric around the bed within 10%. The system saves labor cost and time. This versatile system can be modified and used to compare management practices, estimate concentration-time indexes for pest control, study chemical movement, degradation, and emissions, and test mathematical models.     

Laboratory degradation studies of bentazone, dichlorprop, MCPA, and propiconazole in Norwegian soils

Laboratory degradation studies were performed in Norwegian soils using two commercial formulations (Tilt and Triagran-P) containing either propiconazole alone or a combination of bentazone, dichlorprop, and MCPA. These soils included a fine sandy loam from Hole and a loam from Kroer, both of which are representative of Norwegian agricultural soils. The third soil was a highly decomposed organic material from the Froland forest. A fourth soil from the Skuterud watershed was used only for propiconazole degradation. After 84 d, less than 0.1% of the initial MCPA concentration remained in all three selected soils. For dichlorprop, the same results were found for the fine sandy loam and the organic-rich soil, but in the loam, 26% of the initial concentration remained. After 84 d, less than 0.1% of the initial concentration of bentazone remained in the organic-rich soil, but in the loam and the fine sandy loam 52 and 69% remained, respectively. Propiconazole was shown to be different from the other pesticides by its persistence. Amounts of initial concentration remaining varied from 40, 70, and 82% in the reference soils after 84 d for the organic-rich soil, fine sandy loam, and loam, respectively. The organic-rich soil showed the highest capacity to decompose all four pesticides. The results from the agricultural soils and the Skuterud watershed showed that the persistence of propiconazole was high. Pesticide degradation was approximated to first-order kinetics. Slow rates of degradation, where more than 50% of the pesticide remained in the soil after the 84-d duration of the experiment, did not fit well with first-order kinetics.     

Liming poultry manures to decrease soluble phosphorus and suppress the bacteria population

Stabilizing phosphorus (P) in poultry waste to reduce P losses from manured soils is important to protect surface waters, while pathogens in manures are an emerging issue. This study was conducted to evaluate CaO and Ca(OH)2 for killing manure bacterial populations (pathogens) and stabilizing P in poultry wastes and to investigate the influence on soils following amendment with the treated wastes. Layer manure and broiler litter varying in moisture content were treated with CaO and Ca(OH)2 at rates of 2.5, 5, 10, and 15% by weight. All treated wastes were analyzed for microbial plate counts, pH, and water-soluble phosphorus (WSP), while a few selected layer manures were analyzed by phosphorus X-ray absorption near edge structure (XANES). A loamy sand and a silt loam were amended with broiler litter and layer manure treated with CaO at rates of 0, 2.5, 5, 10, and 15% and soil WSP and pH were measured at times 1, 8, and 29 d. Liming reduced bacterial populations, with greater rates of lime leading to greater reductions; for example 10% CaO applied to 20% solids broiler litter reduced the plate counts from 793,000 to 6500 mL-1. Liming also reduced the WSP in the manures by over 90% in all cases where at least 10% CaO was added. Liming the manures also reduced WSP in soils immediately following application and raised soil pH. The liming process used successfully reduced plate counts and concerns about P losses in runoff following land application of these limed products due to decreased WSP.     

原油在土壤中迁移及降解的研究

为了解原油在土壤中淋滤及降解的规律，剖析了大庆老油田开发区贮油池土壤含油状况，进行了自然植被不同类型土壤的浇油、室内原油淋滤模拟及栽培试验。结果表明：贮油池土壤原油淋滤深度绝大部分集中在0～30cm，以下原油明显减少（除沙化土壤外）；盐碱土集中在0～10cm；草甸黑钙土集中在0～50cm；柱内油水混合渗透试验，80％集中在0～20cm；原油覆盖土壤表面时清水淋渗较弱，在0～20cm内残留94％；加原油的土壤降解试验，平均降解59．92％，范围为53．94％～62．25％，盆栽试验平均降解61．99％，范围为55.12％～70．68％。     

Ammonia volatilization from surface-applied poultry litter under conservation tillage management practices

Land application of poultry litter can provide essential plant nutrients for crop production, but ammonia (NH(3)) volatilization from the litter can be detrimental to the environment. A multiseason study was conducted to quantify NH(3) volatilization rates from surface-applied poultry litter under no-till and paraplowed conservation tillage managements. Litter was applied to supply 90 to 140 kg N ha(-1). Evaluation of NH(3) volatilization was determined using gas concentrations and the flux-gradient gas transport technique using the momentum balance transport coefficient. Ammonia fluxes ranged from 3.3 to 24% of the total N applied during the winter and summer, respectively. Ammonia volatilization was rapid immediately after litter application and stopped within 7 to 8 d. Precipitation of 17 mm essentially halted volatilization, probably by transporting litter N into the soil matrix. Application of poultry to conservation-tilled cropland immediately before rainfall events would reduce N losses to the atmosphere but could also increase NO(3) leaching and runoff to streams and rivers.     

Remediation of saturated soil contaminated with petroleum products using air sparging with thermal enhancement

Pollutants in the form of non-aqueous phase liquids (NAPLs), such as petroleum products, pose a serious threat to the soil and groundwater. A mathematical model was derived to study the unsteady pollutant concentrations through water saturated contaminated soil under air sparging conditions for different NAPLs and soil properties. The comparison between the numerical model results and the published experimental results showed acceptable agreement. Furthermore, an experimental study was conducted to remove NAPLs from the contaminated soil using the sparging air technique, considering the sparging air velocity, air temperature, soil grain size and different contaminant properties. This study showed that sparging air at ambient temperature through the contaminated soil can remove NAPLs, however, employing hot air sparging can provide higher contaminant removal efficiency, by about 9%. An empirical correlation for the volatilization mass transfer coefficient was developed from the experimental results. The dimensionless numbers used were Sherwood number (Sh), Peclet number (Pe), Schmidt number (Sc) and several physical-chemical properties of VOCs and porous media. Finally, the estimated volatilization mass transfer coefficient was used for calculation of the influence of heated sparging air on the spreading of the NAPL plume through the contaminated soil.     

Evaluation of simplifying assumptions on pesticide degradation in soil

There is evidence that degradation of pesticides in simple laboratory systems may differ from that in the field, but it is not clear which of the simplifications inherent in laboratory studies present serious shortcomings. Laboratory experiments evaluated several simplifying assumptions for a clay loam soil and contrasting pesticides. Degradation of cyanazine [2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile] and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] at fluctuating temperature and moisture was predicted reasonably well based on parameters derived from degradation under constant conditions. There was a tendency for slower degradation of cyanazine and bentazone in soil aggregates of 3 to 5 mm in diameter (DT50 at 15 degrees C and 40% maximum water holding capacity of 25.1 and 58.2 d, where DT50 is the time for 50% decline of the initial pesticide concentration) than in soil sieved to <3 mm (DT50 of 19.1 and 37.6 d), but the differences were not significant for most datasets. Degradation of cyanazine, isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea], and chlorotoluron [3-(3-chloro-p-tolyl)-1,1-dimethylurea] was measured in soil amended with different amounts of lignin. The effect of lignin on degradation was small despite considerable differences in sorption. The DT50 values of cyanazine, isoproturon, and chlorotoluron were 16.2, 18.6, and 33.0 d, respectively, in soil without lignin and 19.0, 23.4, and 34.6 d, respectively, in soil amended with 2% lignin. Degradation of bentazone and cyanazine in repacked soil columns was similar under static and flow conditions with 50.1 and 47.2% of applied bentazone and 74.7 and 73.6% of applied cyanazine, respectively, degraded within 20 d of application. Thus, the assumptions underpinning laboratory to field extrapolation tested here were considered to hold for our experimental system. Additional work is required before general conclusions can be drawn.     

Bioconversion of selenate in methanogenic anaerobic granular sludge

The capacity of anaerobic granular sludge to remove selenate from contaminated wastewater was investigated. The potential of different types of granular sludge to remove selenate from the liquid phase was compared to that of suspended sludge and contaminated soil and sediment samples. The selenate removal rates ranged from 400 to 1500 microg g VSS(-1) h(-1), depending on the source of biomass, electron donor, and the initial selenate concentration. The granular structure protects the microorganisms when exposed to high selenate concentrations (0.1 to 1 mM). Anaerobic granular sludge "Eerbeek," originating from a UASB reactor treating paper mill wastewater, removed about 90, 50, and 36% of 0.1, 0.5, and 1 mM of Se, respectively, from the liquid phase when incubated with 20 mM lactate at 30 degrees C and pH 7.5. Selenite, elemental Se (Se(o)), and metal selenide precipitates were the conversion products. Enrichments from the anaerobic granular sludge "Eerbeek" were able to convert 90% of the 10-mM selenate to Se(o) at a rate of 1505 microg Se(VI) g cells(-1) h(-1), a specific growth rate of 0.0125 g cells h(-1), and a yield of 0.083 g cells mg Se(-1). Both microbial metabolic processes (e.g dissimilatory reduction) as well as microbially mediated physicochemical mechanisms (adsorption and precipitation) contribute to the removal of selenate from the Se-containing medium.     

Effect of organic material on field-scale emissions of 1,3-dichloropropene

Soil fumigation is important for growing many fruits and vegetable crops, but fumigant emissions may contaminate the atmosphere. A large-scale field experiment was initiated to test the hypothesis that adding composted municipal green waste to the soil surface in an agricultural field would reduce atmospheric emissions of the 1,3-dichloropropene (1,3-D) after shank injection at a 133 kg ha(-1) application rate. Three micrometeorological methods were used to obtain fumigant flux density and cumulative emission values. The volatilization rate was measured continuously for 16 d, and the daily peak volatilization rates for the three methods ranged from 12 to 24 μg m(-2) s(-1). The total 1,3-D mass that volatilized to the atmosphere was approximately 14 to 68 kg, or 3 to 8% of the applied active ingredient. This represents an approximately 75 to 90% reduction in the total emissions compared with other recent field, field-plot, and laboratory studies. Significant reductions in the volatilization of 1,3-D may be possible when composted municipal green waste is applied to an agricultural field. This methodology also provides a beneficial use and disposal mechanism for composted vegetative material.     

Ammonia volatilization from marsh-pond-marsh constructed wetlands treating swine wastewater

Ammonia (NH3) volatilization is an undesirable mechanism for the removal of nitrogen (N) from wastewater treatment wetlands. To minimize the potential for NH3 volatilization, it is important to determine how wetland design affects NH3 volatilization. The objective of this research was to determine how the presence of a pond section affects NH3 volatilization from constructed wetlands treating wastewater from a confined swine operation. Wastewater was added at different N loads to six constructed wetlands of the marsh-pond-marsh design that were located in Greensboro, North Carolina, USA. A large enclosure was used to measure NH3 volatilization from the marsh and pond sections of each wetland in July and August of 2001. Ammonia volatilized from marsh and pond sections at rates ranging from 5 to 102 mg NH3-N m(-2) h(-1). Pond sections exhibited a significantly greater increase in the rate of NH3 volatilization (p < 0.0001) than did either marsh section as N load increased. At N loads greater than 15 kg ha(-1) d(-1), NH3 volatilization accounted for 23 to 36% of the N load. Furthermore, NH3 volatilization was the dominant (54-79%) N removal mechanism at N loads greater than 15 kg ha(-1) d(-1). Without the pond sections, NH3 volatilization would have been a minor contributor (less than 12%) to the N balance of these wetlands. To minimize NH3 volatilization, continuous marsh systems should be preferred over marsh-pond-marsh systems for the treatment of wastewater from confined animal operations.     

超声-生化法降解8-羟基喹啉废水的实验研究

本文采用超声-生化(两级好氧)联用的方法,对8-羟基喹啉废水的降解工艺进行了研究。对废水的预处理方法为超声降解法,文中分析了溶液初始浓度、超声时间、超声全程时间以及超声细胞粉碎机的变幅杆直径大小对废水预处理效果的影响。实验结果表明,变幅杆直径为25mm,溶液初始浓度为0.6g/L,超声全程时间在20min,最佳超声时间为2s时降解效率最高,CODcr去除率可以达到40.4%。本实验生化处理方法为普通活性污泥法(两级好氧),一级好氧反应池停留时间选择10h,去除率为69.4%;二级好氧反应池停留时间选择6h,去除率为71.7%。超声-生化(两级好氧)联用对8-羟基喹啉废水处理效果良好,CODcr总去除率达到94.4%。