Simulating herbicide volatilization from bare soil affected by atmospheric conditions and limited solubility in water

A numerical model that simulates pesticide fate was developed to predictthe behavior of triallate after application to a field soil. The model has options that allow water and/ or heat transport and can limit simulated aqueous-phase concentrations to triallate solubility in water. Several methods for describing the volatilization boundary condition were tested to assess the accuracy in predicting the volatilization rate, including an approach that requires no atmospheric information and an approach that couples soil and atmospheric processes. Four scenarios were constructed and simulated, to compare with measured volatilization rates. The peak measured volatilization rate (168 g ha(-1) h(-1)) was most accurately predicted with the scenario that included the most complex model (100 g ha(-1) h(-1)). The simplest model overpredicted the peak rate (251 g ha(-1) h(-1)), and the others underpredicted the peak rate (16-67 g ha(-1) h(-1)). The simulations that limited aqueous solubility provided relatively similar values for the total emissions (21-37% of applied triallate), indicating that simplified models may compare well with measurements (31% of applied). A prospective simulation over a period of 100 days showed that applying triallate to the soil surface would ultimately lead to atmospheric emissions of 80% of the applied material with 6% remaining in soil. Incorporating triallate to a depth of 10 cm would reduce emissions to less than 5% and lead to 41% remaining in soil.     

Chiral signatures show volatilization from soil contributes to polychlorinated biphenyls in grass

Enantiomer fractions (EFs) of PCB 95 and concentrations of PCBs 28/31, 52, 101, 118, 138, 153, and 180 were determined in air. Samples were taken at ~14 day intervals on a vertical gradient at an urban background site in Birmingham U.K. in summer 2009 (114 days) and spring 2010 (84 days). EFs in air at 3 cm height were nonracemic (average 0.453 (2009) and 0.468 (2010)) and differed significantly (p < 0.05) from the racemic EFs in air at 10, 40, 90, and 130 cm. EFs in soil (average 0.452 (2009) and 0.447 (2010)) closely matched those in air at 3 cm, while those in grass (average 0.468 (2009) and 0.484 (2010)) were intermediate between those in soil and the racemic EFs in air at ≥ 10 cm. This implies that at the study site, PCBs volatilize from soil to an extent discernible only at the soil:air interface, and that PCBs in grass arise due to foliar uptake of volatile emissions from soil. Atmospheric concentrations of ΣPCBs increased significantly (p < 0.05) with increasing height. Combined with the chiral signature data, this suggests the influence of PCB emissions from soil on airborne concentrations decreases with altitude, while that of emissions from the built environment increases.     

Pathways and relative contributions to arsenic volatilization from rice plants and paddy soil

Recent studies have shown that higher plants are unable to methylate arsenic (As), but it is not known whether methylated As species taken up by plants can be volatilized. Rice (Oryza sativa L.) plants were grown axenically or in a nonsterile soil using a two-chamber system. Arsenic transformation and volatilization were investigated. In the axenic system, uptake of As species into rice roots was in the order of arsenate (As(V)) > monomethylarsonic acid (MMAs(V)) > dimethylarsinic acid (DMAs(V)) > trimethylarsine oxide (TMAs(V)O), but the order of the root-to-shoot transport index (Ti) was reverse. Also, volatilization of trimethylarsine (TMAs) from rice plants was detected when plants were treated with TMAs(V)O but not with As(V), DMAs(V), or MMAs(V). In the soil culture, As was volatilized mainly from the soil. Small amounts of TMAs were also volatilized from the rice plants, which took up DMAs(V), MMAs(V), and TMAs(V)O from the soil solution. The addition of dried distillers grain (DDG) to the soil enhanced As mobilization into the soil solution, As methylation and volatilization from the soil, as well as uptake of different As species and As volatilization from the rice plants. Results show that rice is able to volatilize TMAs after the uptake of TMAs(V)O but not able to convert inorganic As, MMAs(V) or DMAs(V) into TMAs and that the extent of As volatilization from rice plants was much smaller than that from the flooded soil.     

Diurnal variation of diazinon volatilization: soil moisture effects

Diurnal variations in diazinon volatilization were monitored in three field experiments conducted with differing soil moisture contents. The highest flux rates in all experiments were recorded just after diazinon application, but the magnitudes of those initial rates differed according to the soil moisture content, with wetter soil producing a higher rate: 5.6 × 10(-4) μg cm(-2) min(-1) for initial soil moisture above field capacity, 8.3 × 10(-5) μg cm(-2) min(-1) for initial soil moisture at field capacity, and 2.5 × 10(-5) μg cm(-2) min(-1) for initially very dry soil. Volatilization decreased during the first day in the two experiments with initially wet soils but remained relatively constant in the experiment with initially dry soil. The volatilization rate during the first night for the wettest soil remained about an order-of-magnitude higher than that observed for driest soil. When the surface dried in the experiment conducted at the intermediate water content, the volatilization rate and temporal pattern transitioned and became similar to that observed for the initially dry soil. Around noon of the second day, a daily maximum value was observed in the volatilization rate for wet soil, whereas a minimum value was observed for the dry soil, resulting in an order-of magnitude difference. This study demonstrates the importance of soil moisture on emissions of pesticides to the atmosphere.     

Microbial participation in iodine volatilization from soils

The roles of microorganisms in iodine volatilization from soils were studied. Soils were incubated with iodide ion (I-), and volatile organic iodine species were determined with a gas chromatograph. Iodine was emitted mainly as methyl iodide (CH3I), and CH3I emission was sometimes enhanced by the addition of glucose. Soils were then incubated with a radioactive iodine tracer (125I), and radioiodine emitted from soils was determined. The emission of iodine was enhanced in the presence of yeast extract but was inhibited by autoclaving of soils. The addition of streptomycin and tetracycline, antibiotics that inhibit bacterial growth, strongly inhibited iodine emission, while a fungal inhibitor cycloheximide caused little effect. Forty bacterial strains were randomly isolated from soils, and their capacities for volatilizing iodine were determined. Among these, 14 strains volatilized significant amounts of iodine when they were cultivated with iodide ion. Phylogenetic analysis based on 16S ribosomal DNA sequences showed thatthese bacteria are widely distributed through the bacterial domain. Our results suggest that iodine in soils is methylated and volatilized as CH3I by the action of soil bacteria and that iodine-volatilizing bacteria are ubiquitous in soil environments. The pathway of iodine volatilization by soil bacteria should be important for understanding the biogeochemical cycling of iodine as well as for the assessment of long-lived radioactive iodine (129I) in the environment.     

Solar radiation, relative humidity, and soil water effects on metolachlor volatilization

Pesticide volatilization is a significant loss pathway that may have unintended consequences in nontarget environments. Field-scale pesticide volatilization involves the interaction of a number of complex variables. There is a need to acquire pesticide volatilization fluxes from a location where several of these variables can be held constant. Accordingly, soil properties, tillage practices, surface residue management, and pesticide formulations were held constant while fundamental information regarding metolachlor volatilization (a pre-emergent pesticide) was monitored over a five-year period as influenced by meteorological variables and soil water content. Metolachlor vapor concentrations were measured continuously for 120 h after each application using polyurethane foam plugs in a logarithmic profile above the soil surface. A flux gradient technique was used to compute volatilization fluxes from metolachlor concentration profiles and turbulent fluxes of heat and water vapor (as determined from eddy covariance measurements). Differences in meteorological conditions and surface soil water contents resulted in variability of the volatilization losses over the years studied. The peak volatilization losses for each year occurred during the first 24 h after application with a maximum flux rate in 2001 (1500 ng m(-2) s(-1)) associated with wet surface soil conditions combined with warm temperatures. The cumulative volatilization losses for the 120-hour period following metolachlor application varied over the years from 5 to 25% of the applied active ingredient, with approximately 87% of the losses occurring during the first 72 h. In all of the years studied, volatilization occurred diurnally and accounted for between 43 and 86% during the day and 14 and 57% during the night of the total measured loss. The results suggest that metolachlor volatilization is influenced by multiple factors involving meteorological, surface soil, and chemical factors.     

Effects of dietary nitrogen manipulation on ammonia volatilization from manure from Holstein heifers

Decomposition of livestock manure produces gaseous ammonia. Dietary manipulation is one means to reduce N in manure and ammonia volatilization. The effects of dietary crude protein concentration on N intake, N and urinary urea-N excretion, and ammonia volatilization were measured. Eight Holstein heifers (body weight = 260 to 488 kg) were fed a total mixed ration containing either 9.6 or 11.0% crude protein in a crossover design. Oatlage and concentrate were fed at 77:23 (dry matter basis), and soybean meal was used to alter total dietary crude protein. Seven-day adjustment periods preceded 5-d collection periods. Indwelling urinary catheters were inserted 2 d prior to the collection periods. Daily feces and acidified urine were collected, stirred, and subsampled for total Kjeldahl N, urinary urea N, dry matter, P, K, and ash. Urine collection tubes were split during period 2 to allow for collection of unacidified samples for urea N and total N determinations. Unacidified urine and fecal samples were combined (1:1.3) for collection of volatilized ammonia. Remaining slurries were extracted for total and urea N. Increased dietary crude protein concentration increased N intake, N excretion, urea-N excretion, and N excreted in the urine by the heifers. Dietary manipulation of N intake by reduction of 14.0% (dry matter basis) resulted in a 28.1% decrease in ammonia emission and decreases in the urea N, total N, and percentage N excreted in the urine of 29.6, 19.8, and 7.4%, respectively. Ammonia volatilization was dependent on N quantity and form in the urine.     

Efficiency of urease and nitrification inhibitors in reducing ammonia volatilization from diverse nitrogen fertilizers applied to different soil types and wheat straw mulching

BACKGROUND: Some authors suggest that the absence of tillage in agricultural soils might have an influence on the efficiency of nitrogen applied in the soil surface. In this study we investigate the influence of no‐tillage and soil characteristics on the efficiency of a urease inhibitor (N‐(n‐butyl)thiophosphoric triamide, NBPT) and a nitrification inhibitor (diciandiamide, DCD) in decreasing ammonia volatilization from urea and ammonium nitrate (AN), respectively. RESULTS: The results indicate that ammonia volatilization in soils amended with urea was significantly higher than in those fertilized with AN. Likewise, the main soil factors affecting ammonia volatilization from urea are clay and sand soil contents. While clay impedes ammonia volatilization, sand favours it. The presence of organic residues on soil surface (no‐tillage) tends to increase ammonia volatilization from urea, although this fact depended on soil type. The presence of NBPT in urea fertilizer significantly reduced soil ammonia volatilization. This action of NBPT was negatively affected by acid soil pH and favoured by soil clay content. CONCLUSION: The presence of organic residues on soil surface amended with urea increased ammonia volatilization, and was particularly high in sandy compared with clay soils. Application of NBPT reduced ammonia volatilization although its efficiency is reduced in acid soils. Concerning AN fertilization, there were no differences in ammonia volatilization with or without DCD in no‐tillage soils. Copyright © 2011 Society of Chemical Industry     

纱筒残余氨的扩散过程建模与数值模拟

为准确把握液氨整理后纱筒中残余氨的传质特性,提高氨的回收率与回收速率,首先建立了经综合考虑扩散传质和对流传质机制的传质数学模型,对柱坐标系下的传质方程进行归一化处理,将其转换成易于分析的一维平板类传质方程。然后利用Crank-Nicolson隐式差分法对归一化的传质方程进行差分近似求解,证明了算法的稳定性与收敛性。最后将数值计算结果与实验数据对比,验证模型的正确性。结果表明,提高风速以及减小纱筒外径都可加快氨的挥发,小风速下氨挥发过程是一个近似稳态过程。     

Aging of organochlorine pesticides and polychlorinated biphenyls in muck soil: volatilization, bioaccessibility, and degradation

An organic rich muck soil which is highly contaminated with native organochlorine pesticide (OCs) was spiked with known amounts of (13)C-labeled OCs and nonlabeled polychlorinated biphenyls (PCBs). Spiked soils were aged under indoor, outdoor, and sterile conditions and the change in volatility, surrogate bioaccessibility, and degradation of chemicals was monitored periodically over 730 d. Volatility was measured using a fugacity meter to characterize the soil-air partition coefficient (K(SA) = C(SOIL)/C(AIR)). The fraction of bioaccessible residues was estimated by comparing recoveries of chemical with a mild extractant, hydroxylpropyl-β-cyclodextrin (HPCD) vs a harsh extractant, DCM. K(SA) of the spiked OCs in the nonsterile (Indoor, Outdoor) soils were initially lower and approached the K(SA) of native OCs over time, showing reduction of volatility upon aging. HPCD extractability of spiked OCs and PCBs were negatively correlated with K(SA), which suggests that volatility can be used as a surrogate for bioaccessibility. Degradation of endosulfans, PCB 8 and 28 was observed in the nonsterile soils, and (13)C(6)-α-HCH showed selective degradation of the (+) enantiomer. Enantiomer fractions (EF) in air and HPCD extracts were lower than in nonsterile soils, suggesting greater sequestering of the (+) enantiomer in the soil during microbial degradation.     

Research Watch: Chemical volatilization

Indoor Air.     

Research Watch: PCB volatilization

Sediments.     

Variability of herbicide losses from 13 fields to surface water within a small catchment after a controlled herbicide application

Diffuse losses from agricultural fields are a major input source for herbicides in surface waters. In this and in a companion paper, we present the results of a comprehensive field study aimed at assessing the overall loss dynamics of three model herbicides (i.e., atrazine, dimethenamid, and metolachlor) from a small agricultural catchment (2.1 km2) and evaluating the relative contributions of various fields having different soil and topographical characteristics. An identical mixture of the three model herbicides as well as an additional pesticide for identification of a given field were applied within 12 h on 13 cornfields (total area approximately 12 ha), thus ensuring that the herbicides were exposed to identical meteorological conditions. After the simultaneous application, the concentrations of the compounds were monitored in the soils and at the outlets of three subcatchments containing between 4 and 5 cornfields each. Particular emphasis was placed on the two rain events that led to the major losses of the herbicides. The rank orders of herbicide dissipation in the soils and of the compound-specific mobilization into runoff were the same in all three subcatchments and were independent of the field characteristics. In contrast, the field properties caused the relative losses from two subcatchments to differ by up to a factor of 56 during the most important event, whereas compound-specific differences of the three neutral herbicides caused the losses to vary only by a factor of 2 during the same event. The enormous spatial variability was mainly caused by factors influencing the fraction of rain that was lost to surface water by fast transport mechanisms. Thus, the key factors determining the spatially variable herbicide losses were the permeability of the soils, the topography, and the location of subsurface drainage systems. These results illustrate the large potential to reduce herbicide losses by avoiding application on risk areas.     

Arsenic speciation and volatilization from flooded paddy soils amended with different organic matters

Arsenic (As) methylation and volatilization in soil can be increased after organic matter (OM) amendment, though the factors influencing this are poorly understood. Herein we investigate how amended OM influences As speciation as well as how it alters microbial processes in soil and soil solution during As volatilization. Microcosm experiments were conducted on predried and fresh As contaminated paddy soils to investigate microbial mediated As speciation and volatilization under different OM amendment conditions. These experiments indicated that the microbes attached to OM did not significantly influence As volatilization. The arsine flux from the treatment amended with 10% clover (clover-amended treatment, CT) and dried distillers grain (DDG) (DDG-amended treatment, DT2) were significantly higher than the control. Trimethylarsine (TMAs) was the dominant species in arsine derived from CT, whereas the primary arsine species from DT2 was TMAs and arsine (AsH(3)), followed by monomethylarsine (MeAsH(2)). The predominant As species in the soil solutions of CT and DT2 were dimethylarsinic acid (DMAA) and As(V), respectively. OM addition increased the activities of arsenite-oxidizing bacteria (harboring aroA-like genes), though they did not increase or even decrease the abundance of arsenite oxidizers. In contrast, the abundance of arsenate reducers (carrying the arsC gene) was increased by OM amendment; however, significant enhancement of activity of arsenate reducers was observed only in CT. Our results demonstrate that OM addition significantly increased As methylation and volatilization from the investigated paddy soil. The physiologically active bacteria capable of oxidization, reduction, and methylation of As coexisted and mediated the As speciation in soil and soil solution.     

Determination of herbicide residues in agricultural crops, foods, soil and water by chronometric method

Summary The method described is based on the biochemical detection of herbicides on a silica gel thin layer following their chromatographic separation. The detection reagent is a mixture of a homogenate of bean leaves (Phaseolus vulgaris) and of the redox indicator 2,6-dichloroindophenol. This chronometric determination of herbicide residues is based on the observation that dark blue inhibition zones appear on a pale yellow-green background during the exposure of the sprayed chromatoplates Silufol to light. The dark blue zones disappear again after a time, their lifetime is proportional to the amount of the herbicide in the zone.Because of the high selectivity and sensitivity of the biochemical detection this method does not require a multiple clean-up procedure, nor does it require sophisticated instrumentation. It equals gas chromatography in sensitivity and precision. The determination limit lies between 0.01 and 0.001 mg · kg^–1, the average recovery rate is 85 to 90%.

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Bestimmung der Herbicid-Rückstände in landwirtschaftlichen Produkten, in Lebensmitteln, im Boden und Wasser mit der chronometrischen Methode

Zusammenfassung Die Methode stützt sich auf einen biochemischen Nachweis der Herbicide auf einer Silicagel-Dünnschichtplatte nach ihrer chromatographischen Verteilung. Das Nachweisreagens ist eine Mischung aus einem Homogenat von Blättern der Bohnen (Phaseolus vulgaris, L.) und des Redoxindikators 2,6-Dichlorphenolindophenol. Die chronometrische Bestimmung der Herbicidrückstände gründet sich auf die Beobachtung, daß während der Lichtexposition der besprühten Dünnschichtplatte Silufol auf einem gelbgrünen Hintergrund dunkelblaue Inhibitionszoneu entstehen, welche nach einer bestimmten Zeit verschwinden. Die Haltbarkeitszeit der Zone ist der Menge des Herbicids in der Zone direkt proportionell.In Betracht der hohen Selektivität und Empfindlichkeit des biochemischen Nachweises benötigt die Methode keine komplizierte Reinigung der Extrakte und keine hochentwickelte Ausstattung des Labors mit Instrumenten. Die Empfindlichkeit und Genauigkeit der chronometrischen Methode ist gleich der der Gaschromatographie. Die Bestimmungsgrenze ist 0,01 bis 0,001 mg·kg^–1, die Wiederfindung ist 85–90%.

     

Effects of long-term herbicide use,irrigation and nitrogen fertiliser on soil fertility in an apple orchard

In 1972 an experiment was set up to investigate the long-term effects of herbicide, irrigation and two rates of nitrochalk fertiliser application on soil fertility in a Cox's Orange Pippin apple orchard. Samples taken in 1986 showed that uncultivated soil which had been maintained bare by herbicide had much lower organic C, total N and extractable K and Mg concentrations than soil which had been maintained under grass. Extractable P concentrations were lower in soil under grass than in soil under herbicide. In the absence of grass, soil pH was slightly lower than in its presence. All these effects were much greater at depths above 7·5 cm than below. Irrigation of the grass slightly increased organic C and total N levels at 0–7·5 cm compared with unirrigated grass but had no effect on extractable P, K and Mg. Increasing the fertiliser rate from 63 to 189 kg N ha^?1 had no effect on organic C, total N, extractable P and K. Yet, throughout the soil profile, extractable Mg concentrations were greater at the low than at the high N fertiliser rate. In a seedling growth test on soil taken from the orchard in 1988 (and confirmed to be free from residual herbicide), apple seedlings grown in soil which had previously been under grass grew significantly better than those in soil which had been bare. These differences were ascribed to a greater rate of N mineralisation in the soil formerly under grass. The results of this trial indicate that to safeguard soil fertility it is necessary to maintain a grass cover in the orchard. In addition, fertiliser application on newly planted trees should be adjusted to take account of the presence or absence of grass in the previous soil management treatment.