Comparison of screening methods for the estimation of adsorption coefficients on soil

The HPLC screening method for estimating soil sorption coefficients was compared to other QSAR approaches based on log P_ow, connectivity indices, molar refraction and molecular fragment approaches. For the data set under consideration (66 compounds from different chemical classes) only the HPLC screening method and, to a lesser extend, the log P_ow method proved to be suitable for predicting soil sorption coefficients with acceptable accuracy. The HPLC method and the regression with log P_ow were then cross-validated.     

Time dependent sorption behavior of dinotefuran,imidacloprid and thiamethoxam

Dinetofuran (DNT), imidacloprid (IMD) and thiamethoxam (THM) are among the neonicotinoid insecticides widely used for managing insect pests of agricultural and veterinary importance. Environmental occurrence of neonicotinoid in post-application scenario poses unknown issues to human health and ecology. A sorption kinetic study provides much needed information on physico-chemical interaction of neonicotinoid with soil material. In this research study, time-dependent sorption behavior of DNT, IMD and THM in vineyard soil was studied. Sorption kinetics studies were conducted over a period of 96 hours with sampling duration varying from 0, 2, 4, 8, 12, 24, 60 and 96 hours. All three neonicotinoids exhibited very low sorption potential for the soil investigated. Overall percent sorption for all three neonicotinoids was below 20.04 ± 2.03% with highest percent sorption being observed for IMD followed by DNT and THM. All three neonicotinoids are highly soluble with solubility increasing with IMD < THM < DNT. Although, DNT has the highest solubility among all three neonicotinoids investigated, it exhibited higher percent sorption compared to THM, indicating factors other than solubility influenced the sorption kinetics. Low sorption potential of neonicotinoids indicates greater leaching potential with regard to groundwater and surface water contamination.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg(-1) degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg(-1) application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to >70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of (14)C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative (14)CO(2) was less than 1.5% of applied (14)C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Ecotoxicity of imidacloprid to soil invertebrates in two tropical soils with contrasting texture

Environmental Science and Pollution Research - Imidacloprid is one of the most commercialized insecticides in agriculture in the world, with a broad spectrum of action. However, little is known...     

Comparison of two methods for obtaining degradation half-lives

Given the paucity of experimental degradation half-life data for most organic chemicals, there is a compelling incentive to use available estimation software when undertaking assessments of chemical persistence and mass balance modeling studies. In this study, half-life data obtained from estimation software for a set of 233 organic chemicals in air, water, soil and sediments were shown to differ significantly from half-life data listed in handbooks. It is suggested that the widely available and used estimation software, EPIWIN (Estimations Program's Interface for Windows), overestimates the reactivity of persistent organic pollutants (POPs). Reasons for this overestimation are explored. It is concluded that the maximum "default half-life values" used by the EPIWIN software are too short for estimating half-lives of highly persistent chemicals such as PCBs. There is a need for estimation software such as EPIWIN to be more thoroughly calibrated against experimental derived half-life data for a wide range of chemicals, including potential POPs, thus improving their reliability.     

Comparison of two estimation methods for surface area concentration using number concentration and mass concentration of combustion-related ultrafine particles

Recent research has suggested that the adverse health effects caused by nanoparticles are associated with their surface area (SA) concentrations. In this study, SA was estimated in two ways using number and mass concentrations and compared with SA (SA_meas) measured using a diffusion charger (DC). Aerosol measurements were made twice: once starting in October 2002 and again starting in December 2002 in Mysore, India in residences that used kerosene or liquefied petroleum gas (LPG) for cooking. Mass, number, and SA concentrations and size distributions by number were measured in each residence. The first estimation method (SA_PSD) used the size distribution by number to estimate SA. The second method (SA_INV) used a simple inversion scheme that incorporated number and mass concentrations while assuming a lognormal size distribution with a known geometrical standard deviation. SA_PSD was, on average, 2.4 times greater (range = 1.6–3.4) than SA_meas while SA_INV was, on average, 6.0 times greater (range = 4.6–7.7) than SA_meas. The logarithms of SA_PSD and SA_INV were found to be statistically significant predictors of the logarithm of SA_meas. The study showed that particle number and mass concentration measurements can be used to estimate SA with a correction factor that ranges between 2 and 6.     

Agro-waste biosorbents: Effect of physico-chemical properties on atrazine and imidacloprid sorption

Low cost agro-waste biosorbents namely eucalyptus bark (EB), corn cob (CC), bamboo chips (BC), rice straw (RS) and rice husk (RH) were characterized and used to study atrazine and imidacloprid sorption. Adsorption studies suggested that biosorbents greatly varied in their pesticide sorption behaviour. The EB was the best biosorbent to sorb both atrazine and imidacloprid with K_F values of 169.9 and 85.71, respectively. The adsorption isotherm were nonlinear in nature with slope (1/n) values <1. The Freundlich constant Correlating atrazine/imidacloprid sorption parameter [K_F.(1/n)] with the physicochemical properties of the biosorbents suggested that atrazine adsorption correlated significantly to the aromaticity, polarity, surface area, fractal dimension, lacunarity and relative C-O band intensity parameters of biosorbents. Probably, both physisorption and electrostatic interactions were responsible for the pesticide sorption. The eucalyptus bark can be exploited as low cost adsorbent for the removal of these pesticides as well as a component of on-farm biopurification systems.     

Sorption and degradation of imidacloprid in soil and water

Imidacloprid, the major component of many widely used insecticide formulations, is highly persistent in soils. In this study, the sorption of imidacloprid by six soils as well as its photodegradation and hydrolysis in water were studied. The soils differed significantly in organic matter content and other physical and chemical properties. Sorption increased with increasing soil organic matter content but was not significantly correlated with other soil properties. Removal of organic matter via H2O2 oxidation decreased the sorption. By normalizing the Freundlich coefficients (Kf) to organic matter contents, the variability in obtained sorption coefficient (Kom) was substantially reduced. These results indicate that soil organic matter was the primary sorptive medium for imidacloprid. The low heat of sorption calculated from Kom suggests that partition into soil organic matter was most likely the mechanism. The photodegradation and hydrolysis of imidacloprid in water followed pseudo-first-order kinetics; however, the latter process needed a six-time-higher activation energy. While both processes produced the same main intermediate, they occurred via different pathways. The hydrolysis of imidacloprid was not catalyzed by the high interlayer pH in the presence of metal-saturated clays, which appeared to result from the lack of the pesticide adsorption in the interlayers of clays.     

Biodegradation of imidacloprid by an isolated soil microorganism

Imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine), a chloronicotinyl insecticide used to control biting and sucking insects, is very persistent in the soil with a half-life often greater than 100 days. Although a few soil metabolites have been reported in the literature, there are no reports of imidacloprid-degrading soil microorganisms. Our objectives were to discover, isolate, and characterize microorganisms capable of degrading imidacloprid in soil. Two soil-free stable enrichment cultures in N-limited media were obtained that degraded 19 mg L(- 1) (43%) and 11 mg L(- 1) (16%) of the applied imidacloprid, and produced about 19 mg L(- 1) 6-chloronicotinic acid in three weeks. Enrichment media without microorganisms had no loss of imidacloprid. Strain PC-21, obtained from the enrichment cultures, degraded 37% to 58% of 25 mg L(- 1) imidacloprid in tryptic soy broth containing 1 g L(- 1) succinate and D-glucose at 27 degrees C incubation over a period of three weeks. Trace amounts of NO(3)(-)/NO(2)(-)were produced and six metabolites were characterized by high performance liquid chromatography (HPLC) using (14)C-methylene-imidacloprid and liquid chromatograph-electrospray-mass spectrometer (LC-MS). Two of the metabolites were identified as imidacloprid-guanidine and imidacloprid-urea by HPLC standards and LC-MS. During the experiment, 6-chloronicotinic acid was not produced. Less than 1% of the applied (14)C was incorporated into the microbial biomass and no (14)CO(2) was detected. Strain PC-21, identified as a species of Leifsonia by PCR amplification of a 500 bp sequence of 16s rRNA, cometabolized imidacloprid.     

Hydrolysis and soil sorption of insecticide pyraclofos

The hydrolysis of the insecticide pyraclofos in buffered solutions at pH 5.0, 7.0 and 9.0, and its sorption on four soils of different physicochemical properties were investigated. The results showed that the degradation of pyraclofos in buffered solutions followed pseudo-first-order kinetics. At 40°C, the rate constants for the hydrolysis of pyraclofos at pH 5.0, 7.0 and 9.0 were 0.0214, 0.1293, and 2.1656 d^?1, respectively. Pyraclofos was relatively stable under both acidic and neutral conditions, while it was readily hydrolyzed under basic conditions. The sorption of pyraclofos on four soils was well described by the Freundlich equation. The sorption constant, K _f, increased with an increase in soil organic carbon content, suggesting that organic carbon content was an important factor affecting sorption. The K _oc values for Xiaoshan clay loam soil, Hangzhou I clay loam soil, Hangzhou II soil, and Fuyang silt loam soil were 30.4, 6.7, 5.3, and 7.1, respectively. These results suggest that the sorption of pyraclofos on the tested soils was relatively weak.     

Hydrolysis and soil sorption of insecticide pyraclofos

The hydrolysis of the insecticide pyraclofos in buffered solutions at pH 5.0, 7.0 and 9.0, and its sorption on four soils of different physicochemical properties were investigated. The results showed that the degradation of pyraclofos in buffered solutions followed pseudo-first-order kinetics. At 40 degrees C, the rate constants for the hydrolysis of pyraclofos at pH 5.0, 7.0 and 9.0 were 0.0214, 0.1293, and 2.1656 d(-1), respectively. Pyraclofos was relatively stable under both acidic and neutral conditions, while it was readily hydrolyzed under basic conditions. The sorption of pyraclofos on four soils was well described by the Freundlich equation. The sorption constant, K(f), increased with an increase in soil organic carbon content, suggesting that organic carbon content was an important factor affecting sorption. The K(oc) values for Xiaoshan clay loam soil, Hangzhou I clay loam soil, Hangzhou II soil, and Fuyang silt loam soil were 30.4, 6.7, 5.3, and 7.1, respectively. These results suggest that the sorption of pyraclofos on the tested soils was relatively weak.     

水生植物总氮测定中两种消化方法的比较

水生植物在人工湿地污水净化过程中起着非常重要的作用,植物组织中氮、磷的含量是考察人工湿地净化污水效能的一个重要指标。采用经典的Kjeldahl（凯氏）消化法和H2SO4—H2O2消化法测定了人工湿地植物体中总氮含量,分析了两种消化方法各自的优缺点,并应用SPSS统计软件对两种方法测得的数据进行统计检验。其结果表明,两种方法测得的总氮含量具有显著性差异。应根据不同的实验要求选择适宜的测定方法。     

Fate of imidacloprid in soil and plant after application to cotton seeds

This study aimed to investigate the persistence of imidacloprid in soil after application to cotton seeds and to obtain a complete picture on the mass balance of this compound in soil and cotton plants. The study was carried out as a pot culture experiment under laboratory conditions using a Gaucho formulation containing ¹⁴C-labeled imidacloprid. Three treatments of cotton seeds were made in sandy loamy soil: live seeds grown in autoclaved soil, dead seeds put in live soil and live seeds grown in live soil. Results showed that total ¹⁴C recoveries decreased by time ranging 93.8–96.2, 77.1–88.4 and 53.5–62.4% of the applied radioactivity at 7, 14, and 21 d after application, respectively. The reduction in the extracted ¹⁴C from soil coincided with the increase of non-extracted ones. Levels of bound ¹⁴C was always less in autoclaved soil than in live ones. Results revealed also that only 1.8–6.8% of the applied ¹⁴C was taken up by the plants and fluctuated within the test period. ¹⁴C levels were higher in plants grown in autoclaved soil than those in live ones and the radioactivity tended to accumulate on the edges of cotton leaves. Most of the radioactivity in the soil extracts was identified as unchanged ¹⁴C-imidacloprid.     

Characterization and growth response of bacteria in soil following application of carbofuran.

Enhanced biodegradation of carbofuran (2, 3-dihydro-2, 2 dimethyl-7-benzofuranyl methyl carbamate) is an economically significant, but poorly understood, microbial phenomenon in soil. A series of experiments was conducted to examine short term changes in soil bacterial populations stimulated by carbofuran application at field rates. In the field experiment, commercially formulated carbofuran and butylate (S-ethyl diisobutyl carbamothioate) were applied at 5.6 kg ai ha-1 and 8.4 kg ai ha-1, respectively, on a soil (Putnam silt loam) exhibiting enhanced degradation of carbofuran. In laboratory studies, technical grade carbofuran (20 mg kg-1 soil) was applied to samples of the field soil. Bacterial populations were estimated using non-selective (tryptic soy agar) and selective media containing carbofuran or butylate. Largest population increases in pesticide-treated soil were observed between 7 and 15 days after treatment (DAT) compared to populations in non-treated soil. Significant increases (P less than 0.05) in total bacterial populations and presumed carbofuran-degraders due to carbofuran application were associated with increased populations of Pseudomonas spp. and Flavobacterium spp. Application of carbofuran appeared to provide a competitive advantage to these species over actinomycetes persisting beyond 20 DAT. Growth responses of bacteria to carbofuran in the Putnam soil were compared to those in a native prairie soil (Mexico silt loam), which exhibited a much slower rate of carbofuran degradation. Bacterial population response to carbofuran was measurable, but small and short-lived. Perpetuation of the enhanced degradation phenomenon may lie in a persistent pesticide-induced competitive advantage given to a very small segment of the microbial population. This advantage may not be detectable after 20 days using conventional plating techniques.     

The equilibria of bisolute sorption on soil

The goal of this study was to investigate the effects of both concentration levels and loading sequence or contamination history of each pollutant on the equilibrium sorption of mixed organic pollutants on soils. We measured binary sorption equilibria for a soil using ten concentration levels for both phenanthrene and naphthalene. Both solutes were either simultaneously loaded or sequentially loaded (i.e., the second sorbate was loaded after the sorption of the first sorbate had attained equilibrium) on soil. The results showed different competitive sorption equilibria between phenanthrene and naphthalene. In the presence of phenanthrene and regardless of loading sequence, naphthalene exhibited consistently lower sorption capacities and the ideal adsorbed solution theory (IAST) slightly underestimates the naphthalene sorption equilibria. Conversely, the sorption equilibria of phenanthrene in the presence of naphthalene depended upon the loading sequence of the two sorbates on the soil. Little competition from naphthalene on the sorption equilibria of phenanthrene was observed when phenanthrene was loaded either simultaneously with or sequentially after naphthalene, but appreciable competition from naphthalene was observed when the soil had been pre-contaminated with phenanthrene. IAST slightly underestimates the phenanthrene sorption equilibria observed in the latter system, but it cannot estimate the phenanthrene sorption equilibria in the former two systems. We proposed that adsorption on internal surfaces of ink-bottle shaped pores within relatively flexible sorbent matrix may have caused the competitive sorption phenomena observed in this study. The study suggests that contamination history may have strong influence on the equilibrium sorption of organic pollutant mixtures.     

Preliminary study on persistence in soil and residues in maize of imidacloprid

The aim of this work was to study the distribution of imidacloprid in soil and its translocation to roots and aerial parts of maize plant. The main objective was to assess imidacloprid residues in field environment, in order to provide data on honeybees exposure level to such an active substance. Imidacloprid has been detected and quantified by Triple Quadrupole HPLC-MS-MS. Pesticide persistence in the soil and its residues in pollen and in maize plants have been evaluated during the growing of maize plants developed from seeds dressed with Gaucho 350 FS (imidacloprid: 1.0 mg/seed). The sowing has been performed by means of a pneumatic precision drill. Samples have been collected at 30, 45, 60, 80, 130 days after the sowing, as pollen samples have been collected at the tasseling. Imidacloprid presence in aerial part of maize plant declined to 2-3 μg/kg 80 days after the sowing, while concentration in kernel at harvest was <1 μg/kg. Maize pollen represents an important part of protein supply of beehives, and it is of critical importance to bee foraging. The values detected (imidacloprid residues <1 μg/kg) showed that maize pollen source should not be relevant for acute toxicity impact on honey bees.     

Comparison of nonideal sorption formulations in modeling the transport of phthalate esters through packed soil columns

Sorption of dimethyl phthalate (DMP), diethyl phthalate (DEP) and dipropyl phthalate (DPP) to two soil materials that vary in organic matter content was investigated using miscible displacement experiments under saturated flow conditions. Generated breakthrough curves (BTCs) were inversely simulated using linear, equilibrium sorption (LE), nonlinear, equilibrium sorption (NL), linear, first-order nonequilibrium sorption (LFO), linear, radial diffusion (LRD), and nonlinear, first-order nonequilibrium sorption (NFO) models. The Akaike information criterion was utilized to determine the preferred model. The LE model could not adequately describe phthalate ester (PE) BTCs in higher organic matter soil or for more hydrophobic PEs. The LFO and LRD models adequately described the BTCs but a slight improvement in curve-fitting was gained in some cases when the NFO model was used. However, none of the models could properly describe the desorptive tail of DPP for the high organic matter soil. Transport of DPP through this soil was adequately predicted when degradation or sorption hysteresis was considered. Using the optimized parameter values along with values reported by others it was shown that the organic carbon distribution coefficient (K(oc)) of PEs correlates well with the octanol/water partition coefficient (K(ow)). Also, a strong relationship was found between the first-order sorption rate coefficient normalized to injection pulse size and compound residence time. A similar trend of timescale dependence was found for the rate parameter in the radial diffusion model. Results also revealed that the fraction of instantaneous sorption sites is dependent on K(ow) and appears to decrease with the increase in the sorption rate parameter.     

QSPR study on soil sorption coefficient for persistent organic pollutants

Quantitative structure-property relationship (QSPR) models of soil sorption coefficients for 32 persistent organic pollutants were constructed using our recently introduced Lu index and novel distance-based atom-type DAI topological indices. Using multiple linear regression technique, a 6-variable model was obtained with the correlation coefficient of estimations (R) being 0.95, and the standard error of estimations (s) being 0.23, and the correlation coefficient (R(cv)) and the standard error (s(cv)) in the leave-4-out cross-validation procedure are 0.90 and 0.31, respectively. The results in this study indicate that soil sorption coefficients of POPs are dominated by molecular size while some DAI indices have smaller influence.     

Effect of soil properties on degradation and sorption of methyl bromide in soil

Methyl bromide (CH₃Br) is currently the most widely used soil fumigant, and its emission into the atmosphere after application reportedly contributes to ozone depletion in the stratosphere. Irreversible degradation and partially reversible sorption reactions affect the quantity of this furnigant reaching the soil surface and escaping into the atmosphere. Incubation studies in closed headspace vials under controlled conditions showed that degradation of CH₃Br was highly dependent on soil organic matter content, and to a lesser extent, on the moisture level in the soil. Methylation of CH₃Br on organic matter was suggested to be the major reaction that CH₃Br undergoes in the soil environment. Other soil constituents such as clay did not contribute to the degradation under moist or air-dried conditions, though enhanced degradation was observed on oven-dried montmorillonite and kaolinite clays. Within soil profiles, degradation of CH₃Br decreased with soil depth mainly due to the reduction of soil organic matter content with depth. In both Greenfield and Wasco sandy loams, the degradation rate of CH₃Br in soil layers from 0 to 270 cm could be estimated from soil organic matter content. Sorption of CH₃Br on moist soils was generally limited, and varied with soil depth. The degree of sorption could be predicted from soil moisture alone or soil moisture and organic matter content.     

Source estimation methods for atmospheric dispersion

Both forward and backward transport modeling methods are being developed for characterization of sources in atmospheric releases of toxic agents. Forward modeling methods, which describe the atmospheric transport from sources to receptors, use forward-running transport and dispersion models or computational fluid dynamics models which are run many times, and the resulting dispersion field is compared to observations from multiple sensors. Forward modeling methods include Bayesian updating and inference schemes using stochastic Monte Carlo or Markov Chain Monte Carlo sampling techniques. Backward or inverse modeling methods use only one model run in the reverse direction from the receptors to estimate the upwind sources. Inverse modeling methods include adjoint and tangent linear models, Kalman filters, and variational data assimilation, among others.This survey paper discusses these source estimation methods and lists the key references. The need for assessing uncertainties in the characterization of sources using atmospheric transport and dispersion models is emphasized.