Dissolution kinetics of sub-millimeter Composition B detonation residues: role of particle size and particle wetting

The dissolution of the 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from microscale particles (<250 μm) of the explosive formulation Composition B was examined and compared to dissolution from macroscopic particles (>0.5 mm). The dissolution of explosives from detonation soot was also examined. The measured mass transfer coefficients for the microscale particles were one to two orders of magnitude greater than the macroscopic particles. When normalized to particle surface area, mass transfer coefficients of microscale and macroscale particles were similar, indicating that the bulk dissolution processes were similar throughout the examined size range. However, an inverse relationship was observed between the particle diameter and the RDX:TNT mass transfer rate coefficient ratio for dry-attritted particles, which suggests that RDX may be more readily dissolved (relative to TNT) in microscale particles compared to macroscale particles. Aqueous weathering of larger Composition B residues generated particles that possessed mass transfer coefficients that were on the order of 5- to 20-fold higher than dry-attritted particles of all sizes, even when normalized to particle surface area. These aqueous weathered particles also possessed a fourfold lower absolute zeta-potential than dry-attritted particles, which is indicative that they were less hydrophobic (and hence, more wettable) than dry-attritted particles. The increased wettability of these particles provides a plausible explanation for the observed enhanced dissolution. The wetting history and the processes by which particles are produced (e.g., dry physical attrition vs. aqueous weathering) of Composition B residues should be considered when calculating mass transfer rates for fate and transport modeling.     

The toxicity of soil samples containing TNT and other ammunition derived compounds in the enchytraeid and collembola-biotest

The effect of ammunition-like compounds and armament waste on the mortality and reproduction of terrestrial invertebrates was assayed by using two biotests: the enchytraeid-biotest withEnchytraeus crypticus and the collembola-biotest withFolsomia Candida. Toxicity was investigated by using standard soil (Lufa 2.2) spiked with 2,4,6-trinitrotoluene (TNT), hexahydro-l,3,5-trinitro-l,3,5-triazine (hexogen, RDX), octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (octogen, HMX) and 2,4,6-triaminotoluene (TAT). Ecotoxicity was investigated with ammunition-contaminated soil material from the former ammunition plant “Tanne” at Clausthal-Zellerfeld (CTNTla) and the Brandplatz (incineration site) in Torgau-Elsnig (TETNT1a), Germany. TNT increased mortality and reduced reproduction of both test organisms corresponding to the concentrations used, whereas hexogen, octogen and TAT had no effect in the tested concentrations (1000-2000 mg/kg). From the two soil materials, TETNT1a was much more toxic than CTNT1a. The LC50(7d) in the enchytraeid-biotest was 570 mg TNT/kg and the EC50(28d) 369 mg TNT/kg soil material (dw). In the collembola-biotest the LC50(7d) was 185 mg TNT/kg and the EC50(28d) 110 mg TNT/kg soil matter (dw).     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Comparison of biotic and abiotic treatment approaches for co-mingled perchlorate, nitrate, and nitramine explosives in groundwater

Biological and abiotic approaches for treating co-mingled perchlorate, nitrate, and nitramine explosives in groundwater were compared in microcosm and column studies. In microcosms, microscale zero-valent iron (mZVI), nanoscale zero-valent iron (nZVI), and nickel catalyzed the reduction of RDX and HMX from initial concentrations of 9 and 1 mg/L, respectively, to below detection (0.02 mg/L), within 2 h. The mZVI and nZVI also degraded nitrate (3 mg/L) to below 0.4 mg/L, but none of the metal catalysts were observed to appreciably reduce perchlorate ( approximately 5 mg/L) in microcosms. Perchlorate losses were observed after approximately 2 months in columns of aquifer solids treated with mZVI, but this decline appears to be the result of biodegradation rather than abiotic reduction. An emulsified vegetable oil substrate was observed to effectively promote the biological reduction of nitrate, RDX and perchlorate in microcosms, and all four target contaminants in the flow-through columns. Nitrate and perchlorate were biodegraded most rapidly, followed by RDX and then HMX, although the rates of biological reduction for the nitramine explosives were appreciably slower than observed for mZVI or nickel. A model was developed to compare contaminant degradation mechanisms and rates between the biotic and abiotic treatments.     

Measurement of effective air diffusion coefficients for trichloroethene in undisturbed soil cores

In this study, we measure effective diffusion coefficients for trichloroethene in undisturbed soil samples taken from Picatinny Arsenal, New Jersey. The measured effective diffusion coefficients ranged from 0.0053 to 0.0609 cm2/s over a range of air-filled porosity of 0.23-0.49. The experimental data were compared to several previously published relations that predict diffusion coefficients as a function of air-filled porosity and porosity. A multiple linear regression analysis was developed to determine if a modification of the exponents in Millington's [Science 130 (1959) 100] relation would better fit the experimental data. The literature relations appeared to generally underpredict the effective diffusion coefficient for the soil cores studied in this work. Inclusion of a particle-size distribution parameter, d10, did not significantly improve the fit of the linear regression equation. The effective diffusion coefficient and porosity data were used to recalculate estimates of diffusive flux through the subsurface made in a previous study performed at the field site. It was determined that the method of calculation used in the previous study resulted in an underprediction of diffusive flux from the subsurface. We conclude that although Millington's [Science 130 (1959) 100] relation works well to predict effective diffusion coefficients in homogeneous soils with relatively uniform particle-size distributions, it may be inaccurate for many natural soils with heterogeneous structure and/or non-uniform particle-size distributions.     

土壤粒径及有机质对多溴二苯醚热脱附的影响

在实验室条件下,研究了土壤粒径与土壤有机质含量对多溴二苯醚(PBDEs)热脱附的影响,以期为PBDEs污染土壤热脱附修复提供理论依据。实验结果表明,300℃停留30 min条件下,粒径为<75、75～125、125～250、250～425和425～850μm的土壤中PBDEs去除率分别为49.53%、73.88%、79.39%、83.56%和87.09%,PBDEs总去除率随粒径的增大而增大,土壤BDE209较BDE206、BDE207和BDE208更易于脱除。此外,温度低于450℃时,H2O2氧化部分去除有机质后土壤中PBDEs的去除率较原土高;表明,土壤有机质可能抑制土壤中PBDEs的热脱附。     

The influences of ambient particle composition and size on particle infiltration in Los Angeles, CA, residences

Particle infiltration is a key determinant of the indoor concentrations of ambient particles. Few studies have examined the influence of particle composition on infiltration, particularly in areas with high concentrations of volatile particles, such as ammonium nitrate (NH4NO3). A comprehensive indoor monitoring study was conducted in 17 Los Angeles-area homes. As part of this study, indoor/outdoor concentration ratios during overnight (nonindoor source) periods were used to estimate the fraction of ambient particles remaining airborne indoors, or the particle infiltration factor (FINF), for fine particles (PM2.5), its nonvolatile (i.e., black carbon [BC]) and volatile (i.e., nitrate [NO3-]) components, and particle sizes ranging between 0.02 and 10 microm. FINF was highest for BC (median = 0.84) and lowest for NO3- (median = 0.18). The low FINF for NO3- was likely because of volatilization of NO3- particles once indoors, in addition to depositional losses upon building entry. The FINF for PM2.5 (median = 0.48) fell between those for BC and NO3-, reflecting the contributions of both particle components to PM25. FINF varied with particle size, air-exchange rate, and outdoor NO3- concentrations. The FINF for particles between 0.7 and 2 microm in size was considerably lower during periods of high as compared with low outdoor NO3- concentrations, suggesting that outdoor NO3- particles were of this size. This study demonstrates that infiltration of PM2.5 varies by particle component and is lowest for volatile species, such as NH4NO3. Our results suggest that volatile particle components may influence the ability for outdoor PM concentrations to represent indoor and, thus, personal exposures to particles of ambient origin, because volatilization of these particles causes the composition of PM2.5 to differ indoors and outdoors. Consequently, particle composition likely influences observed epidemiologic relationships based on outdoor PM concentrations, especially in areas with high concentrations of NH4NO3 and other volatile particles.     

Adsorption and thermodynamic parameters of chlorantraniliprole and dinotefuran on clay loam soil with difference in particle size and pH

The behavior of chlorantraniliprole (CAP) and dinotefuran (DNF) insecticides was investigated in clay loam soil, a common type of the Egyptian soil. Effect of temperature, pH and particle size of the soil on the adsorption process was studied. Adsorption isotherm by bulk soil and its constituents; humic acid (HA), clay, silt and sand fractions was measured using batch equilibration technique. The results showed that the adsorption of the insecticides tested was significantly affected by the temperature and was a spontaneous interfacial process in the soil. Freundlich model accurately predicted the adsorption behavior of both insecticides. The interaction between soil and insecticides was endothermic and the highest adsorption for CAP and DNF was obtained at pH 9. However, the effect of pH on the adsorption of DNF was lower than that of CAP. Sorption of CAP and DNF on HA fraction was significantly greater than on clay fraction and bulk soil. In addition, the adsorption was significantly increased with particle size decrease. It could be inferred that the adsorption of CAP and DNF on clay loam soil was physical in nature and greatly influenced by the soil components, pH and temperature.     

The effect of propanil co-application on 2,4-D sorption by soil

The herbicide 2,4-D is often applied as a tank mixture in combination with other herbicide products. However, current information on 2,4-D sorption by soil is largely based on batch-equilibrium experiments without considering the competition of other herbicides for sorption sites by soil. This study quantified the effect of the herbicide propanil on the sorption of 2,4-D in soil. Results indicated that propanil competed with 2,4-D for sorption sites, particularly in soils with an organic carbon content greater than 3.6%. The decrease in 2,4-D sorption by soil, as a result of propanil competition, was most notably for herbicide concentrations that are typical of recommended field rates. We conclude that herbicide co-applications on agricultural fields have the potential to increase the mobility of herbicides in soil.     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 μ g g^{? 1}. The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4–6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

工艺条件对磷回收过程中鸟粪石沉淀颗粒粒径的影响

在鸟粪石沉淀法回收废水中磷的过程中,鸟粪石颗粒的大小将直接影响其沉淀的速率,进而影响鸟粪石的沉淀效果和磷的回收率。本文采用激光粒度分析仪测定鸟粪石的平均粒径,详细考察在小型连续搅拌反应-沉淀磷回收装置中不同的工艺条件下鸟粪石颗粒粒径的变化规律,并结合Stokes公式计算鸟粪石颗粒在废水出口处的沉降速率,为沉淀池的设计提供参考依据。结果表明:鸟粪石的平均粒径在12～25μm之间,沉降速率在5.46×10-5～2.37×10-4m/s之间。随着反应室水力停留时间的延长,鸟粪石颗粒的粒径逐渐增大,当停留时间超过18 min时,颗粒的粒径基本不变;随着沉淀室水力停留时间的延长,鸟粪石颗粒的平均粒径缓慢增大,当停留时间超过70 min后颗粒粒径的变化不大;鸟粪石颗粒的平均粒径在一定程度上受废水中磷初始浓度变化的影响,在磷初始浓度为62～128 mg/L时颗粒的粒径变化不大,当磷浓度为496 mg/L时粒径有较大增加,此时鸟粪石颗粒的沉降速率也大幅度增加;鸟粪石颗粒的平均粒径受pH值的影响不大;随氮磷摩尔比的增大,鸟粪石颗粒的平均粒径略有增加;随镁磷摩尔比的增大,鸟粪石颗粒的平均粒径逐渐减小,沉降速率则有明显的下降。     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 micro g g(-1). The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4-6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

超声处理对活性污泥系统污泥减量效果的研究

在活性污泥系统采用超声波处理剩余污泥以考察污泥减量效果及其对系统处理效果的影响.结果表明:在声能密度0.25～0.50 W/mL范围内,经过1～30 min的超声波处理,系统表观产率显著下降,剩余污泥的产量可以减少20%～50%左右.同时发现,污泥的沉降性能指标SVI有所下降,而污泥的稳定性有所提高,活性污泥系统的出水水质略有不同程度的下降.     

Enhanced heavy metal immobilization in soil by grinding with addition of nanometallic Ca/CaO dispersion mixture

This study investigated the use of a nanometallic Ca and CaO dispersion mixture for the immobilization of heavy metals (As, Cd, Cr and Pb) in contaminated soil. Simple grinding achieved 85-90% heavy metal immobilization, but it can be enhanced further to 98-100% by addition of a nanometallic Ca/CaO dispersion mixture produced by grinding. Observations using SEM-EDS elemental maps and semi-quantitative analysis showed that the amounts of As, Cd, Cr, and Pb measurable on the soil particle surface decrease after nanometallic Ca/CaO treatment. The leachable heavy metal concentrations were reduced after nanometallic Ca/CaO treatment to concentrations lower than the Japan soil elution standard regulatory threshold: <0.01 mg L⁻¹ for As, Cd, and Pb; and 0.05 mg L⁻¹ for Cr. Effects of soil moisture and pH on heavy metal immobilization were not strongly influenced. The most probable mechanisms for the enhancement of heavy metal immobilization capacity with nanometallic Ca/CaO treatment might be due to adsorption and entrapment of heavy metals into newly formed aggregates, thereby prompting aggregation of soil particles and enclosure/binding with Ca/CaO-associated immobile salts. Results suggest that the nanometallic Ca/CaO mixture is suitable for use in immobilization of heavy-metal-contaminated soil under normal moisture conditions.     

超声处理对活性污泥系统污泥减量效果的研究

在活性污泥系统采用超声波处理剩余污泥以考察污泥减量效果及其对系统处理效果的影响.结果表明：在声能密度0.25～0.50 W/mL范围内,经过1～30 min的超声波处理,系统表观产率显著下降,剩余污泥的产量可以减少20%～50%左右.同时发现,污泥的沉降性能指标SVI有所下降,而污泥的稳定性有所提高,活性污泥系统的出水水质略有不同程度的下降.     

The effect of multiple soil applications of disulfoton on enhanced microbial degradation in soil and subsequent uptake of insecticidal chemicals by potato plants

Abstract

Potatoes were grown during 1992 in 2 m² plots of loam which had received 1, 2 or 3 annual treatments of Di‐Syston 15G, equivalent to 3.36 kg AI/ha, in furrow at planting. The presence of enhanced degradative activity to the sulfoxide and sulfone metabolites of disulfoton in the soil treated in the previous two years was confirmed by laboratory tests prior to the 1992 treatments. Soil, seed potato and foliage from the three treatments were analyzed for disulfoton and its sulfoxide and sulfone metabolites for 12 wk following planting/treatment. Disulfoton was the major insecticidal component of the soil, a minor component of the seed piece and was not detected (<0.02 ppm) in potato foliage. Disulfoton concentrations in each of the three substrates sampled were similar for the three treatments. Disulfoton sulfoxide and sulfone were the major insecticidal components of the seed piece and foliage. Their maximum concentrations in 1st year soil, seed pieces and foliage were ca. 2x, 2x and 6x, respectively, those measured in the 2nd and 3rd year treatments. The results demonstrate that enhanced microbial degradation of relatively minor insecticidal compounds in the soil can profoundly affect insecticide levels in the plant when these compounds are the major insecticidal components accumulated. The broader implications for crop protection using soil‐applied systemic insecticides are discussed.     

Assessing washing methods for reduction of pesticide residues in Capia pepper with LC-MS/MS

Abstract

The effects of washing treatments on removal rates of some pesticides residues (acetamiprid, chlorpyrifos and formetanate hydrochloride) on pepper were investigated. Method verification was conducted through spiking pepper samples at 0.1, 1.0 and 10.0 × MRL. QuEChERS method produced average recovery of 104.91% with relative standard deviation (RSD) of 13.41%. LOQ values of acetamiprid, chlorpyrifos and formetanate hydrochloride were estimated as 2, 10 and 5?µg/kg, respectively. Capia peppers grown in open fields were sprayed three times with pesticides. Peppers were harvested after 1st, 2nd and 3rd day of the treatments. Then the peppers were subjected to tap water, acetic acid and citric acid washing and ultrasonic cleaning treatments (for 2 and 5?min). Based on three different harvest times and two different washing durations, processing factors (PFs) and reduction rates were calculated for each washing treatment. The residues gradually decreased during washing treatments with increasing process duration. Similarly, a gradual reduction was noted with the progress of harvest times. This in turn corresponded to an increase in PF. Ultrasonic cleaning and citric acid (9%) washing were more effective than the others. Non-systemic pesticides (chlorpyrifos) were more readily removed than the systemic ones (acetamiprid). Similarly, highly soluble pesticides exhibited higher reduction.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

The effect of nitrogen form on rhizosphere soil pH and zinc phytoextraction by Thlaspi caerulescens

The phytoextraction of Zn may be improved by applying N fertilizers to increase the biomass and Zn content of shoots. Rhizosphere-pH change from uptake of different N forms will affect Zn phyto-availability in the rhizosphere and Zn phytoextraction. This glasshouse study examined the effect of N form on Zn phytoextraction by Thlaspi caerulescens (Prayon). The plants were grown in a Zn-contaminated soil (total Zn 250 mg kg-1 soil; pHwater 5.7) and supplied with (NH4)2SO4, Ca(NO3)2 or urea [(NH2)2CO]. The form was maintained by applying the nitrification inhibitor dicyandiamide. A biodegradable chelator ethylenediaminedisuccinic acid (EDDS) was included for comparison. The addition of N doubled the shoot biomass. The highest shoot Zn content occurred in the Ca(NO3)2 treatment and was associated with the highest rhizosphere pH. The lowest shoot dry weight occurred in the EDDS treatment. The Zn concentration in the shoots increased as the rhizosphere pH increased. A significant correlation occurred between Ca and Zn concentrations in the shoots. This study demonstrated that Ca(NO3)2 is a more effective treatment than , urea or EDDS for enhancing Zn phytoextraction in a mildly acidic soil.     

Molecularly imprinted polymers for the detection of benomyl residues in water and soil samples

Benomyl is a benzimidazol fungicide used against various crop pathogens. Although banned in many countries, it is still widely used worldwide and is listed in different monitoring programs among the substances to be monitored to assess human exposure to pesticide residues. The assessment of benomyl is mainly based on the analysis of the residues of its most important metabolite, carbendazim. Existing methods often lack of selectivity and display a limited performance because of the presence of co-extracted compounds. Molecularly imprinted polymers (MIPs) offer an alternative methodology, adsorbing preferentially those target molecules for which the polymers are specifically prepared. In this study, we optimized the synthesis of a polymer imprinted with benomyl. Tests of specificity recognition showed a good performance for carbendazim compared with other similar pesticides. The mean recovery of benomyl (measured as carbendazim) from water samples was estimated to be 90% for MIPs while with real soil samples collected in Morocco the recovery efficiency was 62%. Preliminary tests also suggest that this MIP can implement traditional SPE techniques for assessing benomyl residual concentrations in environmental samples.