Speciation of organic phosphorus in a sediment profile of Lake Taihu II. Molecular species and their depth attenuation

The understanding of organic phosphorus(P) dynamics in sediments requires information on their species at the molecular level,but such information in sediment profiles is scarce.A sediment profile was selected from a large eutrophic lake,Lake Taihu(China),and organic P species in the sediments were detected using solution phosphorus-31 nuclear magnetic resonance spectroscopy(31 P NMR) following extraction of the sediments with a mixture of 0.25 mol/L NaOH and 50 mmol/L EDTA(NaOH-EDTA) solution.The results showed that P in the NaOH-EDTA extracts was mainly composed of orthophosphate,orthophosphate monoesters,phospholipids,DNA,and pyrophosphate.Concentrations of the major organic P compound groups and pyrophosphate showed a decreasing trend with the increase of depth.Their half-life times varied from 3 to 27 years,following the order of orthophosphate monoesters > phospholipids DNA > pyrophosphate.Principal component analysis revealed that the detected organic P species had binding phases similar to those of humic acid-associated organic P(NaOH-NRP HA),a labile organic P pool that tends to transform to recalcitrant organic P pools as the early diagenetic processes proceed.This demonstrated that the depth attenuation of the organic P species could be partly attributed to their increasing immobilization by the sediment solids,while their degradation rates should be significantly lower than what were suggested in previous studies.     

Degradation of rizazole in water–sediment systems

This study investigated the degradation of rizazole in water-sediment systems (West Lake system, WL; Beijing–Hangzhou Grand Canal system, BG) with two different types of sediments under aerobic and anaerobic conditions. The half-lives of rizazole in the WL water phase (14.59–15.13 d) were similar to those in the BG water phase (15.90–16.46 d). Within 3–7 d, the rizazole concentration in the sediments reached the maximum values, i.e., equilibrium. Rizazole dissipation was faster in the WL sediment phase with higher organic matter content (T_1/2 = 18.99–19.09 d) compared with the BG sediment phase (T_1/2 = 31.08–33.32 d). Rizazole degradation was slightly faster in the West Lake water-sediment system (WL system) (T_1/2 = 17.11–18.05 d) than in the Beijing–Hangzhou Grand Canal water—sediment system (BG system) (T_1/2 = 20.51–25.02 d). The aerobic degradation of rizazole was similar to its anaerobic degradation in the water-sediment system. The findings are useful to understand the behavior of pesticide in environment.     

Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program

Background, aims, and scope  Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. Materials and methods  Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment’s areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. Results  The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g⁻¹ lw): 4–95 in lipid of planktovores and 7–150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21–31 in Themisto libellula (chatka), 26–42 in Boreocadus saida (Polar cod), and 5–27 in Gadus morhua (cod) liver. Discussion  The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. Conclusions  Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment’s environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. Recommendations and perspectives  For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area. This article is dedicated to the memory of Professor Alexander B Terentiev (who passed away in November 2006), our true friend. With his Institute of Organo-Element Compounds, Russian Academy of Science, Moscow, he was an important main organizer of the six joint Finnish–Russian seminars (every third year since 1989) on the field (‘Chemistry and Ecology of Organo-Element Compounds’). He prompted us especially to search properties and environmental fates for various polyhalogen compounds. We remember him for his friendly character and great sense of humor.     

Development of controlled release formulations of azadirachtin-A employing poly(ethylene glycol) based amphiphilic copolymers

Controlled release (CR) formulations of azadirachtin-A, a bioactive constituent derived from the seed of Azadirachta indica A. Juss (Meliaceae), have been prepared using commercially available polyvinyl chloride, polyethylene glycol (PEG) and laboratory synthesized poly ethylene glycol–based amphiphilic copolymers. Copolymers of polyethylene glycol and various dimethyl esters, which self assemble into nano micellar aggregates in aqueous media, have been synthesized. The kinetics of azadirachtin-A, release in water from the different formulations was studied. Release from the commercial polyethylene glycol (PEG) formulation was faster than the other CR formulations. The rate of release of encapsulated azadirachtin-A from nano micellar aggregates is reduced by increasing the molecular weight of PEG. The diffusion exponent (n value) of azadirachtin-A, in water ranged from 0.47 to 1.18 in the tested formulations. The release was diffusion controlled with a half release time (t_1/2) of 3.05 to 42.80 days in water from different matrices. The results suggest that depending upon the polymer matrix used, the application rate of azadirachtin-A can be optimized to achieve insect control at the desired level and period.     

Biodegradation of α and β Endosulfan in Soil as Influenced by Application of Different Organic Materials

Abstract

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of α and β endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg^?1. The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for α and β endosulfan isomers by gas chromatography. The results indicated that the half-life (T _½) of α-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T _½ of β-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T _½ was about 115 days for the other three treatments.     

三唑酮在油菜-土壤生态系统中的降解与建模

为评价三唑酮可湿性粉剂在土壤-油菜生态系统中使用后的残留行为和环境安全性,进行了2 a大田试验,并比较了指数模型、GM(1,1)灰色模型、阻滞动力学模型对三唑酮降解规律的描述。结果表明:3种模型的拟合结果均达到统计学意义上显著相关;对三唑酮在土壤和油菜中降解行为模拟结果最好的分别为GM(1,1)模型和阻滞动力学模型;三唑酮在土壤中2 a的半衰期分别为3.48和4.38 d,油菜植株中分别为1.98和3.78 d,其降解受温度影响较大。     

Residues and dissipation kinetic of abamectin,chlorfenapyr and pyridaben acaricides in green beans (Phaseolus vulgaris L.) under field conditions using QuEChERS method and HPLC

Abstract

The current study estimated the dissipation rates of abamectin, chlorfenapyr and pyridaben acaricides in pods of green beans (Phaseolus vulgaris L.) under field conditions in Egypt. Pesticides were extracted and cleaned-up by QuEChERS method and were analyzed by HPLC. The dissipation of these acaricides followed the first order kinetics model with half-life (t_1/2) values 1.00, 3.50 and 1.50?days for abamectin, chlorfenapyr and pyridaben, respectively. The lowest residues, at different time intervals of field application rate of each pesticide, were observed with abamectin followed by pyridaben and then chlorfenapyr. Pre-harvest intervals (PHIs) were 10.00, 13.50 and 6.00?days for abamectin, chlorfenapyr and pyridaben, respectively and were below the established European maximum residue limits (EU MRLs) 10–14, 14–21 and 7–10?days after application, respectively. If the fresh pods will be consumed after harvest, it is expected that the presence of these pesticides in the food will have a negative impact on human health. Therefore, the elimination of the residues of these harmful pesticides must be carried out.     

高效石油降解菌的筛选鉴定及修复能力研究

为了得到高效的石油降解菌,本研究利用以柴油为唯一碳源的培养基从山东胜利油田、新疆克拉玛依油田和陕西长庆油田3处的石油污染土壤中富集纯化出3株高效的石油降解菌,分别命名为WTS、Z3-P和H4-1.测试结果显示,经过10d的降解实验,这3株降解菌对柴油的降解率均达到60%以上,降解效果良好,其中,WTS的降解效率最高,达到75%;用这3株菌进行污染土壤的修复实验,污染土壤中石油烃降解半衰期为30d左右,为自然情况下的1/4左右.对石油降解菌进行生理生化反应鉴定以及细菌16S rRNA鉴定结果表明,WTS是柠檬酸杆菌(Citrobacter sp.),H4-1是木糖氧化产碱菌(Alcaligenes xylosoxydans),Z3-P为芽孢杆菌(Bacillus sp.).     

Environmental fate and ecotoxicology of propanil: a review

The herbicide propanil, a synthetic anilide, was discovered in 1957 to control grasses and broad-leaf weeds in rice fields. It has been found to disrupt the electron transport chain by inhibiting the photosystem II, thus impacting plant growth. In the environment, photolysis represents a major degradation pathway, whereas volatilization is not a major route of dissipation from either water or moist soils. Propanil is rapidly degraded by microbes into the major degradation product 3,4-dichloroaniline. This degradation product has been highly detected in both groundwater and surface waters throughout the world. Propanil has been found to adversely impact many non-target organisms. It is toxic to some early life-stage aquatic organisms, in addition to being moderately toxic to the water flea (Ceriodaphnia dubia) and rainbow trout. In addition, it has been reported to pose a high acute and long-term risk to birds. In plants, growth rates are highly impacted; however, some plant species are becoming resistant to propanil.     

水泥灰三相泡沫的形成机理与稳定性试验研究

针对高硫矿石容易发生氧化自燃的危险,通常的灌浆、注砂、注惰气和喷洒阻化剂等技术还存在一些不足,提出一种以水泥灰为基料的三相泡沫来预防硫化矿石自燃的新技术。该技术是将水泥灰和水按一定的比例混合,同时加入一定比例的发泡剂和稳泡剂后,经物理机械方式发泡形成,集固、液、气三相材料的防灭火性能与一体。理论分析了水泥灰三相泡沫的形成与衰变机理,并通过正交试验,对三相泡沫的发泡倍数与半衰期进行研究,最后采用单因素实验,定量分析灰水质量比,发泡剂和稳泡剂浓度对三相泡沫稳定性能的影响,得到最佳泡沫配方。结果表明:当灰水质量比为1:5,发泡剂浓度为5g/L,稳泡剂浓度为8g/L时,制得的三相泡沫发泡倍数达到6倍,半衰期达到6h以上。