Controlled release formulations of metribuzin: Release kinetics in water and soil

Controlled release (CR) formulations of metribuzin in Polyvinyl chloride [(PVC) (emulsion)], carboxy methyl cellulose (CMC), and carboxy methyl cellulose-kaolinite composite (CMC-KAO), are reported. Kinetics of its release in water and soil was studied in comparison with the commercial formulation (75 DF). Metribuzin from the commercial formulation became non-detectable after 35 days whereas it attained maxima between 35–49 days and became non-detectable after 63 days in the developed products. Amongst the CR formulations, the release in both water and soil was the fastest in CMC and slowest in PVC. The CMC-KAO composite reduced the rate of release as compared to CMC alone. The diffusion exponent (n value) of metribuzin in water and soil ranged from 0.515 to 0.745 and 0.662 to 1.296, respectively in the various formulations. The release was diffusion controlled with half release time (t_1/2) from different controlled release matrices of 12.98 to 47.63 days in water and 16.90 to 51.79 days in soil. It was 3.25 and 4.66 days, respectively in the commercial formulation. The period of optimum availability of metribuzin in water and soil from controlled released formulations ranged from 15.09 to 31.68 and 17.99 to 34.72 days as against 5.03 and 8.80 days in the commercial formulation.     

Impact of soil amendments on metribuzin and DCPA half-lives and mobility into agricultural runoff water

The retention and behavior of two herbicides, metribuzin [4-amino-6-tert-butyl-4, 5-dihydro-3-methylthio-1, 2, 4-triazin-5-one] and DCPA [1, 4-Benzenedicarboxylic acid, 2, 3, 5, 6-tetrachloro-, dimethyl] ester, in runoff and seepage water from agricultural fields were investigated. The objectives of this investigation were to: (i) determine the dissipation and half-life (T _1/2) of metribuzin and DCPA herbicides in soil under three management practices: chicken manure (CM), sewage sludge (SS), and no-mulch native soil (NM); (ii) monitor herbicides residues in runoff and infiltration water following addition of soil amendments; and (iii) determine the impact of soil amendments on the transport of NO₃, NH₄, and PO₄ from soil into surface and subsurface water. Half-life (T _1/2) values of metribuzin were 24, 18, and 12 d in CM, SS, and NM treatments, respectively. Similarly, T _1/2 values of DCPA were greater in CM and SS incorporated soil (45.8 and 52.2 d, respectively) compared to NM native soil (26.2 d). Addition of CM and SS to native agricultural soil increased water infiltration, lowering runoff water volume and herbicide residues in runoff following natural rainfall events. We concluded that soil amendments could be used to intercept pesticide-contaminated runoff from agricultural fields. This practice might provide a potential solution to pesticide contamination of surface and seepage water from farmlands.     

底泥污染物释放动力学研究

采用模拟试验方式和新型微生物数量测定方法 ,研究了沼泽化湖泊底泥和受污染河流底泥在不同扰动状态下 ,底泥耗氧速率、氮和磷污染物释放动力学过程。结果表明 :( 1)底泥耗氧速率是同样条件下上覆水耗氧速率的 48倍 ,而在扰动状态下 ,底泥耗氧速率达到上覆水耗氧速率的 5 96— 93 6倍 ,扰动底泥显著增大其耗氧速率 ,底泥污染越严重 ,其耗氧速率越大 ,对水体产生的影响也越大。 ( 2 )扰动底泥可以显著增大底泥的氮磷释放速率 ,氮的释放受有机氮的氨化、氨氮的硝化、硝酸盐氮的反硝化以及氨氮被微生物吸收转化为有机氮等的影响 ;磷的释放过程受厌氧过程和底泥颗粒吸附的影响 ,耗氧速率高的底泥具有更大的氮磷释放潜力。 ( 3 )微生物数量在底泥污染物释放动力学中起着关键性作用 ,新型方法可以快速检测微生物总量。试验结果对于水环境的管理、受污染水体的修复 ,以及底泥的处理处置等都具有重要的指导意义     

Kinetics of peat soil dissolved organic carbon release from bed sediment to water. Part 1. Laboratory simulation

Temporary water reservoirs built upon peat soil may exhibit water quality impairment from elevated dissolved organic carbon (DOC). Microbiological decay of the organic carbon in the bed with subsequent release produces "tea" colored water which may require treatment prior to use. This paper describes laboratory experiments designed to obtain data on the release process of DOC from soils containing 0.65%, 10% and 19% carbon. Parallel experiments with and without sodium azide treatment clearly distinguished the initial release of a porewater residual fraction and the microbial produced fraction. A one to two day quick-release DOC fraction, which ranges from 28% to 50%, first emerged from the bed, Step-1. This was followed by a constant rate of DOC production over four weeks, Step-2. The Step-2 average production rates were 3.4, 12, and 31 mg DOC/kg(dry)/day for the respective soils and increased as soil carbon content increased. The inorganic carbon (IC) behaved oppositely; its rate of production decreased with increasing soil carbon. A consistent and simple rate equation described the Step-2 DOC production process. This and other evidence obtained provided the basis for developing a mathematical model that couples both steps of the bed-to-water DOC release chemodynamics. The model is presented in a companion paper (Part-2).     

Kinetics of phenanthrene desorption from activated carbons to water

We determined the kinetics of phenanthrene desorption from three activated carbons to water using Tenax beads as an infinite sink for organic compounds in water. Desorption kinetic data very well fitted a biphasic kinetic model based on the presence of two different adsorption sites, viz. low-energy sites and high-energy sites. Rate constants for desorption to water from these two types of sites in the three activated carbons did not reveal a relation with activated carbon grain size. These rate constants were comparable to those for desorption of various organic compounds from hard carbon in various sediments.     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

热改性净水污泥对水体底泥磷的控释机制

本研究以净水污泥为原料,通过400 ℃、4 h煅烧制备了热改性净水污泥。探讨了其对水体中磷酸盐的吸附特性,以及在不同投加量 (2.5%、5%、10%) 下热改性净水污泥对底泥中磷的控释及形态影响。同时结合SEM、BET等表征手段,探究了WTS_400-4对底泥中磷的稳定机理。结果表明,WTS_400-4相比WTS具有更发达的孔隙结构及比表面积,增强了对磷酸盐的吸附能力。吸附过程符合准二级动力学模型,Freundlich模型更适用于描述WTS_400-4吸附磷酸盐的过程,其中参数n＞1,说明WTS_400-4对磷酸盐的吸附容易进行。WTS_400-4的添加会使底泥中弱吸附态磷(NH₄Cl-P)、氧化还原敏感态磷(BD-P)和有机磷(Org-P)等不稳定态磷向稳定的金属氧化物结合态磷(NaOH-rP)转变,且其转化量会随着WTS_400-4投加量的增加而增加,有助于抑制底泥磷向上覆水释放。此外,WTS_400-4的添加可降低底泥中WSP(水溶性磷)和Olsen-P (碳酸氢钠可提取磷)这2种生物有效磷含量。WTS_400-4添加入底泥,一方面可以降低底泥中潜在活性磷和生物有效磷含量,降低底泥内源磷向上覆水释放的风险,另一方面可以通过WTS_400-4的吸附作用直接去除间隙水中的磷,从而降低上覆水和间隙水之间的磷浓度梯度,进而抑制磷从间隙水向上覆水中释放。结果表明,WTS_400-4可作为底泥改良剂用以控制水体和底泥的磷含量。     

Degradation of metribuzin in two soil types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

Kinetics of disaggregation of humic acid in water

The extent of disaggregation of humic acid particles in water was measured as a function of time, initial concentration, pH of the suspension and the temperature. In all experiments the amount of humic acid particles disaggregated was characterized by the corresponding fraction of the suspension, which was able to pass a 0.01 μm membrane filter.It was found that the amount disaggregated after 1000 hours was proportional to the initial concentration of the humic acid particles in the aqueous suspension and increased considerably with the temperature. Decreasing the pH of the suspension from about 6 to zero caused the extent of disaggregation also to decrease continuously.The kinetic measurements revealed that about 3% of the humic acid are disaggregated within 25 hours, 4% within 200 hours and 5% within 1500 hours at a pH around 4. The rates of disaggregation were found to be proportional to the initial concentration of the particles and increased considerably with the temperature.     

Toxicity persistence in runoff and soil from experimental soybean plots following insecticide applications

Persistence of toxicity in runoff water and soil was investigated in experimental soybean plots subjected to successive runoff events following pesticide application. Runoff events were produced by irrigation using a sprinkler system. The pesticides applied were cypermethrin and endosulfan, which are widely used in soy production in Argentina. Toxicity tests were performed on two abundant components of the regional fauna, the amphipod Hyalella curvispina and the fish Cnesterodon decemmaculatus. Runoffs from two pesticide applications were assayed at different stages of the growing season: an early application when the soil was almost bare and a late one close to harvest, when the ground was covered by vegetation and just before soy leaves fell. Toxicity to H. curvispina in runoff ceased almost one month after the early application of the two pesticides, while it persisted for over three months after the late application. Soil toxicity to H. curvispina and runoff toxicity to C. decemmaculatus followed the same pattern. Higher temperatures and solar radiation are likely to have enhanced insecticide degradation after the early application. Lower temperatures and solar radiation in combination with increased organic matter from litter probably contributed to the longer persistence of toxicity recorded after the late application, as compared with the early application. Cypermethrin caused no mortality to C. decemmaculatus after the early application, while endosulfan toxicity persisted for almost four months after the late one.     

Kinetics of peat soil dissolved organic carbon release to surface water. Part 2. A chemodynamic process model

Temporary water reservoirs built upon peat soil may exhibit water quality impairment from elevated dissolved organic carbon (DOC). Microbiological decay of the organic carbon in the bed with subsequent release produces "tea" colored water which may require treatment prior to use. This paper contains a process-based mathematical model that quantifies the DOC release from the bed and its build-up in the water column. The model elements are based on microbial DOC production rates and bed sediment transport kinetics describing its' release from the organic soil systems. It relies on laboratory data obtained from an experimental study, Part 1, designed to simulate the DOC chemodynamics of aquatic reservoirs built upon peat soils. A two-step DOC release process was structured based on the experimental findings. The model mechanism assumes a quick release fraction that characterizes the upper soil surface layers as a "tea bag" type release process. This is followed by a fraction that is continuously produced and then released at a constant rate overtime by on-going microbial processes within the upper soil layers. The depth of the active layer, selected as h* = 0.3 cm, is the single adjustable parameter in the model. Concentration predictions of the are consistent with the laboratory simulations and field observations. Measured vs. model-calculated DOC concentrations for both in the microcosm bed and water column are used to test critical features of the proposed model. As conceived and structured it appears to be a realistic first step in quantifying the DOC release consequences for the water column of a reservoir sited upon a peat-soil bed. The development ends with an application to a hypothetical reservoir in order to illustrate model strengths and uncertainties.     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

多水源供水管网中铁释放规律

针对水源切换而引起的水质超标现象,开展了多水源联合供水条件下管网中铁释放规律的研究。分析了北方某城市2种水源(滦河水和长江水)的水质特点,利用实验模拟反应器分别研究了水源完全置换和供水分界线处水源混合区域的铁释放规律。结果表明,多水源供水管网的铁释放速率与水源水质密切相关,特别是水中含高浓度SO2-4和氯化物时会加快铁的释放。不同水源之间的频繁切换会破坏管垢表面的钝化层,使铁释放速率迅速变化,随后会有所缓解,但新的平衡的形成需要较长时间。供水分界线处的水源混合区域,由于水质的不断变化造成管垢表面很难形成稳定的钝化层,铁释放速率持续偏高,只有当长江水所占比例高达75%以上时才能得到抑制。     

催化超临界水氧化偏二甲肼动力学研究

采用CuO/γ-Al2O3和MnO2/γ-Al2O3为催化剂、H2O2为氧化剂,在一连续流固定床反应器中进行了催化超临界水氧化偏二甲肼实验,得到了COD去除宏观动力学方程.在24 MPa、400～450℃和H2O2过量的情况下,反应对COD分别为1.11级(CuO)和1.26级(MnO2),对氧气分别为0.10级(CuO)和0.12级(MnO2).反应的活化能分别为35.75 kJ/mol(CuO)和37.79 kJ/mol(MnO2),前置因子A分别为9.35×102(CuO)和3.45 ×103(MnO2).     

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.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15–92%, whereas with the Kota fly ash an increase in sorption by 13–38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K_f/K_d values, K_FA values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

丙烯酸废水超临界水氧化动力学研究

用H2O2作为氧化剂,对丙烯酸生产废水进行超临界水氧化研究.得到了反应速率方程表达式.COD、H2O2和水的反应级数分别为1、0和0,指前因子A为4.97 s-1,反应活化能Ea为20.64 kJ/mol,诱导时间为8 s左右.     

水源切换条件下模拟管网铁离子释放控制

用北京市某供水区域铸铁管段搭建2套模拟管网装置,对水源切换条件下管网铁离子释放的控制进行了研究。实验过程中利用地下水为水源,通过调节进入管网的水中氯浓度为1.0~1.1 mg/L,溶解氧浓度为7~8 mg/L,经过40 d运行后,管垢成分主要为α-FeOOH和Fe3O4。切换地表水源后,新的管垢组成更有助于铁氧化物中铁的氧化还原重新达到平衡,从而可以有效减少水源切换条件下铁离子的释放,管网出水浊度也得到很好的控制,保持了管网水质稳定性。