The effects of pesticide mixtures on degradation of pendimethalin in soils

Most agronomic situations involve a sequence of herbicide, fungicide, and insecticide application. On the other hand, use of pesticidal combinations has become a standard practice in the production of many agricultural crops. One of the most important processes influencing the behavior of a pesticide in the environment is its degradation in soil. It is known that due to several pesticide applications in one vegetation season, the pesticide may be present in mixtures with other pesticides or xenobiotics in soil. This study examines the role which a mixture of chemicals plays in pesticide degradation. The influence of other pesticides on the rate of pendimethalin (PDM) degradation in soil was measured in controlled conditions. Mixtures of PDM with mancozeb or mancozeb and thiamethoxam significantly influenced the degradation of pendimethalin under controlled conditions. The second type of mixtures, with metribuzin or thiamethoxam, did not affect the behavior of pendimethalin in soil. Also, we determined the influence of water content on the rate of pendimethalin degradation alone in two soils and compared it to the rate in three pesticide mixtures. We compared two equations to evaluate the predictors of the rate of herbicide dissipation in soil: the first-order kinetic and the non-linear empirical models. We used the non-linear empirical model assuming that the degradation rate of a herbicide in soil is proportional to the difference of the observed concentration of herbicide in soil at time and concentration of herbicide in the last day of measurement.     

Atrazine Transport Within a Coastal Zone in Southeastern Puerto Rico: a Sensitivity Analysis of an Agricultural Field Model and Riparian Zone Management Model

Agrichemical runoff from farmland may adversely impact coastal water quality. Two models, the Agricultural Policy/Environmental eXtender (APEX) and the Riparian Ecosystem Management Model (REMM), were used to evaluate the movement of the herbicide atrazine to the Jobos Bay National Estuarine Research Reserve from adjacent fields. The reserve is located on Puerto Rico’s southeast coast. Edge-of-field atrazine outputs simulated with the APEX were routed through a grass-forest buffer using the REMM. Atrazine DT₅₀ (half-life) values measured in both field and buffer soils indicated that accelerated degradation conditions had developed in the field soil due to repeated atrazine application. APEX simulations examined both the measured field and buffer soil atrazine DT₅₀ and the model’s default value. The use of the measured field soil atrazine degradation rate in the APEX resulted in 33 % lower atrazine transport from the field. REMM simulations indicated that the buffer system had the potential to reduce dissolved atrazine transport in surface runoff by 77 % during non-tropical storm events by increasing infiltration, slowing transport, and increasing time for pesticide degradation. During a large runoff event due to a tropical storm that occurred close to the time of an atrazine application, the REMM simulated only a 37 % reduction in atrazine transport. The results indicate that large storm events soon after herbicide application likely dominate herbicide transport to coastal waters in the region. These results agree with water quality measurements in the reserve. This study demonstrated the sensitivity of these models to variations in DT₅₀ values in evaluating atrazine fate and transport in the region and emphasizes that the use of measured DT₅₀ values can improve model accuracy.     

Comparison of linuron degradation in the presence of pesticide mixtures in soil under laboratory conditions

It is widely recognised that complex interactions occur between chemicals in mixtures. In many agricultural situations, the use of tank mixes and complex spray programs is a common practice. Insecticides, fungicides and a herbicide being applied in potato protection were used in this research. Interactions between linuron and insecticides, such as thiamethoxam or clothianidin, and fungicides, such as mancozeb or chlorothalonil, were examined in soil. The degradation rate of linuron in soil during laboratory incubation in six treatments was studied. Mixtures of linuron with mancozeb in sandy loam and clay loam soils had a significant effect on the persistence of this herbicide. For example, for the same herbicide, t _1/2 values for linuron were from 37 days in sandy loam to 44 days in clay loam. These values changed (64–67 days) when thiamethoxam and mancozeb were in soil. When mancozeb was added only, the half-life values were from 59 to 62 days, respectively. Other mixtures with chlorothalonil, thiamethoxam and clothianidin did not have any effect. In order to compare linuron degradation rates in soils, a single first-order model and expanded statistical analysis were used.     

Assessment of imidacloprid degradation by soil-isolated Bacillus alkalinitrilicus

Imidacloprid is extensively used on a broad range of crops worldwide as seed dressing, soil treatment, and foliar application. Hence, the degradation potential of bacterial strains from sugarcane-growing soils was studied in liquid medium for subsequent use in bioremediation of contaminated soils. The microbe cultures degrading imidacloprid were isolated and enriched on Dorn’s broth containing imidacloprid as sole carbon source maintained at 28 °C and Bacillus alkalinitrilicus showed maximum potential to degrade imidacloprid. Clay loam soil samples were fortified with imidacloprid at 50, 100, and 150 mg kg^?1 along with 45?×?10⁷ microbe cells under two opposing sets of conditions, viz., autoclaved and unautoclaved. To study degradation and metabolism of imidacloprid under these two conditions, samples were drawn at regular intervals of 7, 14, 28, 35, 42, 49, and 56 days. Among metabolites, three metabolites were detected, viz., 6-chloronicotinic acid, nitrosimine followed by imidacloprid-NTG under both the conditions. Total imidacloprid residues were not found to follow the first-order kinetics in both types of conditions. This paper reports for the first time the potential use of pure cultures of soil-isolated native bacterium B. alkalinitrilicus and also its use along with natural soil microflora for remediation of imidacloprid-contaminated soils.     

Toxic effect caused on microflora of soil by pesticide picloram application

The toxic effect of the herbicide picloram on the microbial population of a typical Brazilian red Latosol soil was studied in a series of microcalorimetric experiments. The activity of the soil was stimulated by the addition of 6.0 mg of glucose and 6.0 mg of ammonium sulfate, under 34.8% controlled moisture, to a 1.50 mg soil sample, at 298.15 +/- 0.02 K. The net thermal effect due to the addition of the picloram to the soil was determined by interpreting the power-time curves, which were recorded on the microcalorimeter. The total thermal effect evolved by the microorganisms was affected by the increasing doses of herbicide, and varied from 0 to 10.00 micrograms g-1. An increase in picloram exposure caused a decrease of the original thermal effect, reaching a null value above 20.89 micrograms of herbicide per gram of soil. The decreases of the thermal effect evolved by microorganisms and the increase of the lag phase period are associated with the death of the microbial population. The effects caused by picloram application in this typical Brazilian soil resulted in a strong effect on the soil microbial communities.     

Fluorescence spectroscopic characterization of dissolved organic matter fractions in soils in soil aquifer treatment

This work investigated the effect of soil aquifer treatment (SAT) operation on the fluorescence characteristics of dissolved organic matter (DOM) fractions in soils through laboratory-scale soil columns with a 2-year operation. The resin adsorption technique (with XAD-8 and XAD-4 resins) was employed to characterize the dissolved organic matter in soils into five fractions, i.e., hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N), and hydrophilic fraction (HPI). The synchronous fluorescence spectra revealed the presence of soluble microbial byproduct- and humic acid-like components and polycyclic aromatic compounds in DOM in soils, and SAT operation resulted in the enrichment of these fluorescent materials in all DOM fractions in the surface soil (0–12.5 cm). More importantly, the quantitative method of fluorescence regional integration was used in the analysis of excitation–emission matrix (EEM) spectra of DOM fractions in soils. The cumulative EEM volume (Φ _{T, n} ) results showed that SAT operation led to the enrichment of more fluorescent components in HPO-A and TPI-A, as well as the dominance of less fluorescent components in HPO-N, TPI-N, and HPI in the bottom soil (75–150 cm). Total Φ _{T, n} values, which were calculated as $ {\Phi_{{T,n}}} \times {\mathrm{DOC}} $ , suggested an accumulation of fluorescent organic matter in the upper 75 cm of soil as a consequence of SAT operation. The distribution of volumetric fluorescence among five regions (i.e., P _{i, n} ) results revealed that SAT caused the increased content of humic-like fluorophores as well as the decreased content of protein-like fluorophores in both HPO-A and TPI-A in soils.     

Enhancement effect of two ecological earthworm species (Eisenia foetida and Amynthas robustus E. Perrier) on removal and degradation processes of soil DDT

Effects of two ecological earthworm species (epigeic Eisenia foetida and endogeic Amynthas robustus E. Perrier) with different densities (15 and 30 individuals per kg of soil) on the removal of soil 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) with two pollution levels (2 and 4 mg kg(-1)) were investigated. Concentrations of DDT and its metabolites, including 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD), 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE), and 1-chloro-2,2-bis(4-chlorophenyl)ethylene (DDMU), were monitored after 60, 180, and 360 days of incubation. The results obtained showed that both earthworm species can significantly enhance degradation of soil DDT to its metabolites. For E. foetida, the higher earthworm density showed significantly higher rate of DDT degradation than the lower one. Anaerobic reductive dechlorination was the main degradation pathway over 180 days of incubation, while the aerobic dechlorination process was promoted between 180 and 360 days of incubation. Some earthworm amended treatments showed significantly higher microbial biomass carbon and nitrogen than the control, which suggested that earthworms might enhance the microbial degradation of DDT. Both earthworm species would have the potential to be applied to enhance the remediation of agricultural lands polluted by DDT.     

Dissipation and residue of 2,4-D isooctyl ester in wheat and soil

A simple analytical method was developed to determine the 2,4-D isooctyl ester residue in wheat and soil by gas chromatography coupled with electron capture detector. Using the method, the dissipation and residue of 2,4-D isooctyl ester in wheat field was investigated. The average recoveries of 2,4-D isooctyl ester ranged from 80.1% to 110.0% with relative standard deviations of 2.4% to 16.1%. The pesticide showed a rapid dissipation rate either in wheat seedling or soil, with the half-lives of 1.0 to 3.0 days. The terminal residue results in wheat grain were much lower than the codex MRL (2.0 mg/kg). It could be considered safe to food and environment when using this herbicide for controlling weeds in wheat field.     

Does road salting induce or ameliorate DOC mobilisation from roadside soils to surface waters in the long term?

Soils down slope of roads have been affected over decades by road salting in the UK uplands. Salt additions to fresh soil facilitate dispersal of organic matter so there is a potential risk of release of DON and DOC to nearby rivers where these run parallel to roads. Over time, however, salting enhances soil pH of naturally acid soils, and thus organic matter degradation through to CO2, thereby, lowering soil organic matter content. In addition any relatively labile organic matter may have already been dispersed. Thus, it is hypothesised that enhanced DOC mobilisation should only be a potential problem if soils not previously exposed to salt become heavily exposed in the future. This paper combines data from field observations and laboratory simulations to elucidate mechanisms controlling organic matter mobilisation processes to determine what controls spatial and temporal trends in DOC concentrations in soil solutions down slope of roads. Organic matter solubilisation is dependent on the degree of road salt exposure soils have had. The laboratory experiment provided evidence that there are two competing effects upon which solubilisation is dependent (a) pH suppression and (b) sodium dispersion. Other organic matter solubility models, if correct, link quite well with the authors "when it's gone, it's gone" hypothesis.     

Quality assurance and quality control data validation procedures used for the Love Canal and Dallas lead soil monitoring programs

Public awareness of soils contamination has increased in recent years due in part to the notoriety associated with the indiscriminate release, packaging, transporting and disposal of hazardous materials. In 1980, and again in 1982, the U.S. Environmental Protection Agency (EPA) was responsible for designing, implementing and conducting environmental monitoring programs at Love Canal in Niagara Falls, New York, and in Dallas, Texas, that dealt with suspected contaminated soils. Both of these monitoring programs were conducted over a relatively short time with the collection and analysis of over 4000 soil samples. The methods employed by the Environmental Protection Agency for providing soil data that was scientifically valid and of defensible quality for each of these monitoring programs are presented. Also, methods for identifying data bias, its precision and its uncertainty are identified.     

Soil water, salt, and groundwater characteristics in shelterbelts with no irrigation for several years in an extremely arid area

This paper is based on long-term monitoring data for soil water, salt content, and groundwater characteristics taken from shelterbelts where there has been no irrigation for at least 5 years. This study investigated the distribution characteristics of soil water and salt content in soils with different textures. The relationships between soil moisture, soil salinity, and groundwater level were analyzed using 3 years of monitoring data from a typical oasis located in an extremely arid area in northwest China. The results showed that (1) the variation trend in soil moisture with soil depth in the shelterbelts varied depending on soil texture. The soil moisture was lower in sandy and loamy shelterbelts and higher in clay shelterbelts. (2) Salinity was higher (about 3.0 mS cm^?1) in clay shelterbelts and lower (about 0.8 mS cm^?1) in sandy shelterbelts. (3) There was a negative correlation between soil moisture in the shelterbelts and groundwater level. Soil moisture decreased gradually as the depth of groundwater table declined. (4) There was a positive correlation between soil salinity in the shelterbelts and the depth of groundwater table. Salinity increased gradually as groundwater levels declined.     

Impacts of epigeic, anecic and endogeic earthworms on metal and metalloid mobility and availability

The introduction of earthworms into soils contaminated with metals and metalloids has been suggested to aid restoration practices. Eisenia veneta (epigeic), Lumbricus terrestris (anecic) and Allolobophora chlorotica (endogeic) earthworms were cultivated in columns containing 900 g soil with 1130, 345, 113 and 131 mg kg(-1) of As, Cu, Pb and Zn, respectively, for up to 112 days, in parallel with earthworm-free columns. Leachate was produced by pouring water on the soil surface to saturate the soil and generate downflow. Ryegrass was grown on the top of columns to assess metal uptake into biota. Different ecological groups affected metals in the same way by increasing concentrations and free ion activities in leachate, but anecic L. terrestris had the greatest effect by increasing leachate concentrations of As by 267%, Cu by 393%, Pb by 190%, and Zn by 429% compared to earthworm-free columns. Ryegrass grown in earthworm-bearing soil accumulated more metal and the soil microbial community exhibited greater stress. Results are consistent with earthworm enhanced degradation of organic matter leading to release of organically bound elements. The degradation of organic matter also releases organic acids which decrease the soil pH. The earthworms do not appear to carry out a unique process, but increase the rate of a process that is already occurring. The impact of earthworms on metal mobility and availability should therefore be considered when inoculating earthworms into contaminated soils as new pathways to receptors may be created or the flow of metals and metalloids to receptors may be elevated.     

Assessment of the effects of Cr, Cu, Ni and Pb soil contamination by ecotoxicological tests

This study aimed to assess soil quality by chemical and ecotoxicological investigations and to check the correspondence between soil metal concentrations and ecotoxicity. For these purposes, surface soils collected at four adjacent roadside urban parks and at a former industrial area were characterized for C/N, organic matter content, texture, and pH. Cr, Cu, Ni and Pb, chosen among the most representative soil metal contaminants, were measured as total content and as available and water soluble fractions. In addition, the total concentrations of the investigated metals were used to calculate two chemical indices: the contamination and the potential ecological risk factors. The toxicity of the investigated soils was evaluated by an ecotoxicity test battery carried out on both soil samples (Vibrio fischeri, Heterocypris incongruens and Sinapis alba) and elutriates (Vibrio fischeri, Daphnia magna and Selenastrum capricornutum). The findings, both by the chemical and ecotoxicological approaches, would suggest that the soils with high metal contamination pose ecological risks. On the other hand, moderately metal contaminated soils did not exclude soil ecotoxicity. In fact, toxic effects were also highlighted in soils with low metal content, toxicity being affected by metal availability and soil characteristics. Moreover, the results suggest the importance of using a battery of tests to assess soil ecotoxicity.     

High heterogeneity in soil composition and quality in different mangrove forests of Venezuela

Mangrove forests play an important role in biogeochemical cycles of metals, nutrients, and C in coastal ecosystems. However, these functions could be strongly affected by the mangrove soil degradation. In this study, we performed an intensive sampling characterizing mangrove soils under different types of environment (lagoon/gulf) and vegetation (Rhizophora/Avicennia/dead mangrove) in the Venezuelan coast. To better understand the spatial heterogeneity of the composition and characteristics of the soils, a wide range of the soil attributes were analyzed. In general, the soils were anoxic (Eh < 200 mV), with a neutral pH and low concentration in toxic metals; nevertheless, they varied widely in the soil and its quality-defining parameters (e.g., clay contents, total organic carbon, Fe, Al, toxic trace metals). It is noteworthy that the mangroves presented a low Fe_Pyrite content due to a limitation in the Fe oxyhydroxide contents, especially in soils with higher organic C content (TOC > 15%). Finally, the dead mangrove showed significantly lower amounts of TOC and fibers (in comparison to the well-preserved mangrove forest), which indicates that the C pools in mangrove soils are highly sensitive also to natural impact, such as ENSO.     

Classification of moisture and aeration regimes in sub-boreal forest soils

One hundred and two white spruce (Picea glauca (Moench) Voss) stands were studied in the Sub-boreal Spruce zone of British Columbia and were quantitatively classified into seven soil moisture regimes (moderately dry, slightly dry, fresh, moist, very moist, wet, and very wet) according to actual/potential evapotranspiration ratio, depth to gleyed layer or prominent mottling, and depth to groundwater table. The delineated soil moisture regimes demonstrated strong relationships with the composition of understory vegetation and white spruce foliar nutrients and site index. These relationships implied that the three differentiating characteristics used in the classification provided a good estimation of growing-season soil water supply. In addition to soil moisture regimes, three soil aeration regimes (adequate, restricted, and deficient) were delineated according to presence or absence of gleyed horizons and groundwater table, slope gradient, and soil texture. These soil aeration regimes helped in explaining the variation in white spruce site index, especially on water-surplus sites. Thus, an integrated classification of soil moisture-aeration regimes was proposed to explain the effect of soil moisture and aeration on white spruce productivity.The results of this study gave further evidence that soil moisture and aeration regimes, differentiated on the basis of climatic data and soil morphological properties, are useful measures of soil moisture and aeration conditions in sub-boreal forest soils.     

The fate and persistence of polychlorinated biphenyls in soil

The fate and persistence of PCBs 28, 52, 101, 138, and 180 artificially introduced into three soils was studied under a variety of field conditions for up to 415 d following initial contamination. A relationship was detected between ln Koa (octanol/air partition coefficient) and the experimentally observed first-order loss rate constant that was statistically significant at at least the 90% level in all but one instance. In nearly all experiments, PCB persistence was greater in soils of higher organic carbon content. Soil temperature and moisture content were also indicated as important influences on persistence. Significantly longer half-lives were observed in a soil in which initial PCB contamination had occurred ca. 1 year previously. A mass balance showed the most likely mechanism of loss to be volatilisation. Losses attributable to aerobic biodegradation could not be ruled out, but those due to leaching, uptake by biota, and soil erosion were demonstrated to be negligible. First-order rate constants (Kv) were determined for volatilisation of the same congeners from soil under a variety of controlled laboratory scenarios. Multiple linear regression analysis (MLRA) showed the most important influences on kv to be ln Koa (adjusted for soil temperature) and soil organic carbon content. Limited evidence was observed for a relationship between kv and soil moisture content, but not water flux. When tested against field measurements, the MLRA-derived relationship between kv and independent variables predicted to within a factor of 2.5, the persistence of PCBs 28, 52, and 101, However, it did not account for the influence of the age of contaminant association with the soil, soil moisture content or water flux, and failed to function for soils of high organic content, or where ln Koa exceeds ca. 23.     

STUMOD—a Tool for Predicting Fate and Transport of Nitrogen in Soil Treatment Units

A typical onsite wastewater treatment system consists of a septic tank and a soil treatment unit to treat wastewater before it is discharged through the vadose zone to an aquifer. A tool was developed for the purpose of predicting the fate and transport of nitrogen in soil treatment units (STUMOD or Soil Treatment Unit Model). STUMOD calculates nitrogen species concentrations and the fraction of total nitrogen reaching the aquifer or a specified soil depth. Input data include parameters for hydraulics and nutrient transport and transformation. An analytical solution is used to calculate the profile of pressure based on Darcy’s equation and the relationships between suction head, unsaturated hydraulic conductivity, and soil moisture. Chemical transport is based on simplification of the advection–dispersion equation. STUMOD is relatively simple to use but accounts for important processes such as ammonium sorption, nitrification, and denitrification. STUMOD accounts for the effect of soil moisture content (a surrogate for redox conditions) on nitrification and denitrification reactions. The model has provisions to handle the influence of temperature and organic carbon content on nitrogen transformation. Model outputs, generated based on input parameters obtained from extensive literature review, were compared to a numerical model and data from laboratory tests and field sites. Both measured data and STUMOD outputs show a relatively higher removal in clayey soils compared to sandy soils. Consistent with literature data for most soils, STUMOD predicted ammonium conversion to nitrate within the first foot below the trench infiltrative surface.     

土壤重金属监测过程及其质量控制

重点探讨了土壤中典型重金属含量监测过程中样品制备、含水率、预处理等因素对分析结果的影响。实验结果表明,充分风干土壤的含水率在2%～3%左右,200目土壤颗粒度可满足分析精度的要求。硝酸-氢氟酸-高氯酸的多元混酸消解体系可实现对土壤重金属的充分溶解,对标准土壤样品中各元素的回收率可达84%～98%。批次内平行样品以及批次间质控样品各元素的相对标准偏差大都小于10%,符合《土壤环境监测技术规范》的要求,表明该研究建立的系统土壤重金属检测方法结果准确可靠。     

An analytical model for the assessment of pesticide exposure levels in soils and groundwater

The movement and degradation of pesticide residues in soils and groundwater are complex processes affected by soil physical, (bio)chemical, and hydrogeological properties, climatic conditions, and agricultural practices. This work presents a physically-based analytical model suitable for long-term predictions of pesticide concentrations in groundwater. The primary interest is to investigate the impact of soil environment, related physical and (bio)chemical processes, especially, volatilization, crop uptake, and agricultural practices on long-term vulnerability of groundwater to contamination by pesticides. The soil is separated into root and intermediate vadose zones, each with uniform properties. Transport in each soil zone is modeled on the basis of complete mixing, by spatial averaging the related point multiphase-transport partial differential equation (i.e., linear-reservoir models). Transport in the aquifer, however, is modeled by a two-dimensional advection-dispersion transport equation, considering adsorption and first-order decay rate. Vaporization in the soil is accounted for by assuming liquid-vapor phase partitioning using Henry's law, and vapor flux (volatilization) from the soil surface is modeled by diffusion through an air boundary layer. Sorption of liquid-phase solutes by crops is described by a linear relationship which is valid for first-order (passive) crop uptake. The model is applied to five pesticides (atrazine, bromacil, chlordane, heptachlor, and lindane), and the potential for pesticide contamination of groundwater is investigated for sandy and clayey soils. Simulation results show that groundwater contamination can be substantially reduced for clayey soil environments, where bio(chemical) degradation and volatilization are most efficient as natural loss pathways for the pesticides. Also, uptake by cross can be a significant mechanism for attenuating exposure levels in ground-water especially in a sandy soil environment, and for relatively persisting pesticides. Further, simulations indicate that changing agricultural practices can have a profound effect on vulnerability of groundwater to mobile and relatively persisting pesticides.     

Effects of temperature and soil moisture on methyl halide and chloroform fluxes from drained peatland pasture soils

A series of laboratory-based incubations using a stable isotope tracer technique was applied to measure the net and gross fluxes of CH(3)Cl and CH(3)Br as well as the net fluxes of CHCl(3) from surface soils of the Sacramento-San Joaquin Delta of California. Annually averaged flux measurements show that these mineral/oxidized peat soils are a net source of CH(3)Cl (140 ± 266 nmol m(-2) d(-1)) and CHCl(3) (258 ± 288 nmol m(-2) d(-1)), and a net sink of CH(3)Br (-2.3 ± 4.5 nmol m(-2) d(-1)). Gross CH(3)Cl and CH(3)Br fluxes are strongly influenced by both soil moisture and temperature: gross production rates of CH(3)Cl and CH(3)Br are linearly correlated with temperature, whereas gross consumption rates exhibit Gaussian relationships with maximum consumption at soil moisture levels between 20 and 30% volumetric water content (VWC) and a temperature range of 25 to 35 °C. Although soil moisture and soil temperature strongly affect consumption rates, the range of gross consumption rates overall is limited (-506 ± 176 nmol m(-2) d(-1) for CH(3)Cl and -12 ± 4 nmol m(-2) d(-1) for CH(3)Br) and is similar to rates reported in previous studies. CHCl(3) fluxes are not correlated with methyl halide fluxes, temperature, or soil moisture. The annual emission rates of CHCl(3) from the Sacramento-San Joaquin Delta are found to be a potentially significant local source of this compound.