Kinetics of metribuzin release from bentonite-polymer composites in water

A series of bentonite polymer-composites (BPCs) loaded with metribuzin were studied for their controlled release in aqueous medium. The release of active ingredient from BPCs was significantly lower as compared to commercial metribuzin formulation. The results revealed that the cumulative metribuzin release was highest (81%) from the BPCs containing 8% clay (commercial bentonite) and 2% metribuzin which correspond to the lowest (14 days) half-life values i.e., time required for 50% release of active ingredient (t_1/2). The metribuzin release from the BPCs decreased with increased concentration of clays in polymer matrix and the release was further decreased with BPCs prepared with pure nano-bentonite. BPCs containing 12% clay and 2% metribuzin showed maximum t_1/2 values i.e., 25 and 51 days for commercial bentonite and pure nano-bentonite as clay sources, respectively. The differential behaviour in the metribuzin release rates from BPCs was ascribed due to variations in crosslinking of metribuzin in the composites. As metribuzin release was found to be slower in BPCs compared to commercial formulation, it could be used for control of weeds tailored to different crops.     

Prevention of chloridazon and metribuzin pollution using lignin-based formulations

The herbicides chloridazon and metribuzin, identified as groundwater pollutants, were incorporated in lignin-based granules with different sizes to obtain controlled release formulations (CRFs) and reduce water pollution risk. Kinetics release tests in water and soil showed that the release rate of both from CRFs diminished in comparison to technical products. A linear correlation was obtained between the time taken for 50% of the active ingredient to be released (T₅₀) into water and granule size of the CRFs. Besides, a linear correlation was reached between T₅₀ values in water and soil. Mobility experiments carried out in calcareous soil show that the use of lignin-based CRFs reduces the presence of both herbicides in the leachate compared to the technical grade products. The set of experiments developed in this research can be useful to design, prepare and evaluate formulations with CR properties which can reduce the pollution derived from the use of herbicides.     

控制释放技术与水的消毒保质

介绍了控制释放技术及其在水消毒保质方面的应用 ,指出了控制释放技术在水消毒保质方面的优越性、重要意义及应用前景     

Development of controlled release formulations of thiram employing amphiphilic polymers and their bioefficacy evaluation in seed quality enhancement studies

Controlled release formulations of Thiram (Dimethylcarbamothioylsulfanyl-N,N-dimethylcarbamodithioate), a contact fungicide, have been prepared using laboratory synthesized poly(ethylene glycol) (PEG) based functionalized amphiphilic copolymers. The kinetics of thiram from developed controlled release (CR) formulations were studied in comparison with that of the commercially available 75 WS. Release from the commercial formulation was faster than with the developed CR formulations. Maximum amount of thiram was released on 35th day for PEG-2000 4d, 28th day for PEG-1500 4c, 21st day for PEG-1000 4b and 15th day for PEG-600 4a in comparison to commercial formulation (7th day). The diffusion exponent (n) of thiram in water ranged from 0.356 to 0.545 in the tested formulations. The half-release (t_1/2) values ranged between 14.78 to 22.1 days, and the Period of Optimum Availability (POA) of thiram ranged from 7.79 to 25.15 days. An effort has also been made to identify the suitable polymers that could reduce the seed deterioration during storage and also act as an effective carrier of fungicide thiram. The results demonstrate that the seeds coated with the different formulations deteriorated at a slower pace as manifested in high germination percentage over control. Apart from the fungicidal effect of thiram, the polymers acted as barriers to moisture reducing the rate of seed deterioration and checked the degradation of thiram. The CR formulation 4d, with PEG 2000, was found to be most effective as seed coat.     

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。     

Release behavior and bioefficacy of imazethapyr formulations based on biopolymeric hydrogels

Controlled release formulations of imazethapyr herbicide have been developed employing guar gum-g-cl-polyacrylate/bentonite clay hydrogel composite (GG-HG) and guar gum-g-cl-PNIPAm nano hydrogel (GG-NHG) as carriers, to assess the suitability of biopolymeric hydrogels as controlled herbicide release devices. The kinetics of imazethapyr release from the developed formulations was studied in water and it revealed that the developed formulations of imazethapyr behaved as slow release formulations as compared to commercial formulation. The calculated diffusion exponent (n) values showed that Fickian diffusion was the predominant mechanism of imazethapyr release from the developed formulations. Time for release of half of the loaded imazethapyr (t_1/2) ranged between 0.06 and 4.8 days in case of GG-NHG and 4.4 and 12.6 days for the GG-HG formulations. Weed control index (WCI) of GG-HG and GG-NHG formulations was similar to that of the commercial formulation and the herbicidal effect was observed for relatively longer period. Guar gum-based biopolymeric hydrogels in both macro and nano particle size range can serve as potential carriers in developing slow release herbicide formulations.     

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.     

Eco-friendly PEG-based controlled release nano-formulations of Mancozeb: Synthesis and bioefficacy evaluation against phytopathogenic fungi Alternaria solani and Sclerotium rolfsii

Controlled release (CR) nano-formulations of Mancozeb (manganese-zinc double salt of N,N-bisdithiocarbamic acid), a protective fungicide, have been prepared using laboratory-synthesized poly(ethylene glycols) (PEGs)-based functionalized amphiphilic copolymers without using any surfactants or external additives. The release kinetics of the developed Mancozeb CR formulations were studied and compared with that of commercially available 42% suspension concentrate and 75% wettable powder. Maximum amount of Mancozeb was released on 42nd day for PEG-600 and octyl chain, PEG-1000 and octyl chain, and PEG-600 and hexadecyl chain, on 35th day for PEG-1000 and hexadecyl chain, on 28th day for PEG-1500 and octyl chain, PEG-2000 and octyl chain, PEG-1500 and hexadecyl chain, and PEG-2000 and hexadecyl chain in comparison to both commercial formulations (15th day). The diffusion exponent (n value) of Mancozeb in water ranged from 0.42 to 0.62 in tested formulations. The half-release (t_1/2) values ranged from 17.35 to 35.14 days, and the period of optimum availability of Mancozeb ranged from 18.54 to 35.42 days. Further, the in vitro bioefficacy evaluation of developed formulations was done against plant pathogenic fungi Alternaria solani and Sclerotium rolfsii by poison food technique. Effective dose for 50% inhibition in mgL^?1 (ED₅₀) values of developed formulations varied from 1.31 to 2.79 mg L^?1 for A. solani, and 1.60 to 3.14 mg L^?1 for S. rolfsii. The present methodology is simple, economical, and eco-friendly for the development of environment-friendly CR formulations of Mancozeb. These formulations can be used to optimize the release of Mancozeb to achieve disease control for the desired period depending upon the matrix of the polymer used. Importantly, the maximum amount of active ingredient remains available for a reasonable period after application. In addition, the developed CR formulations were found to be suitable for fungicidal applications, allowing use of Mancozeb in lower doses.     

表面活性剂CMC对石油烃污染土壤的增溶

研究了表面活性剂羧甲基纤维素钠（carboxyl methyl cellulose,CMC）对土壤中石油污染物的增溶作用。通过批实验,对比研究了CMC和十二烷基苯磺酸钠SDBS 2种表面活性剂的增溶效果,探究了CMC浓度、pH、盐度及回用次数对土壤中石油烃增溶效果的影响。研究结果表明,当CMC浓度为0.5%,增溶时间为24 h时,对TPHs浓度为17 695 mg·kg-1的污染土样,TPHs洗脱率高达60%以上。碱性环境有利于石油烃的洗脱,酸性体系会抑制石油烃的洗脱;增溶作用随盐度的增大而显著增大。在利用CMC对污染土壤进行增溶洗脱时,对于TPHs高浓度污染土壤,可以选择将其洗脱液回用1次或者2次;对于TPHs较低浓度污染土壤,可以选择将其洗脱液回用于较高浓度的污染土壤。     

沛沿河流域土壤肥料释放的降雨模拟研究

为有效控制农业面源污染,改善沛沿河流域水质状况,通过对水稻田、杨树林和果园的土壤分别施用不同类型化肥后,模拟研究了土壤在受雨水短期浸泡及连续降雨情况下氮、磷的释放特征。研究结果表明,稻田土壤对氮磷的保肥能力最佳,施肥时应以基肥为主;果园土壤及林地土壤的保肥能力均劣于稻田土壤,应采用少量多次追肥的方法。尿素与碳铵宜做基肥使用,而氯化铵与硫酸铵宜做追肥使用。     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg^?1, the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day^?1 and the total amount of 2,4-D mineralized at 130 days (M₁₃₀) ranged from 24 to 39%. Both k and M₁₃₀ were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M₁₃₀ were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.     

Development of controlled release nanoformulations of carbendazim employing amphiphilic polymers and their bioefficacy evaluation against Rhizoctonia solani

Controlled release nanoformulations of carbendazim (Methyl 1H-benzimidazol-2-ylcarbamate), a systemic fungicide, have been prepared using laboratory synthesized poly(ethylene glycols) (PEGs)-based functionalized amphiphilic copolymers. The release kinetics of carbendazim from developed controlled release (CR) formulations was studied and compared with that of the commercially available 50% Wettable Powder (WP). Further, the bioefficacy evaluation of developed formulations was done against plant pathogenic fungi Rhizoctonia solani by the poison food technique method. The release of maximum amount of carbendazim from developed formulations was dependent on the molecular weight of PEGs and was found to increase with increasing molecular weights. The range of carbendazim release was found to be between 10th to 35th day as compared to commercial formulation which was up to 7th day. The diffusion exponent (n value) of carbendazim in water ranged from 0.37 to 0.52 in the tested formulations. The half-release (t_1/2) values ranged between 9.47 and 24.20 days, and the period of optimum availability (POA) of carbendazim ranged from 9.15 to 26.63 days. Also, ED₅₀ values of the developed formulations vary from 0.40 to 0.74 mg L^?1. These formulations can be used to optimize the release of carbendazim to achieve disease control for the desired period depending on the matrix of the polymer used.     

Controlled release and retarded leaching of pesticides by encapsulating in carboxymethyl chitosan /bentonite composite gel

A novel composite gel composed of carboxymethyl-chitosan (CM-chit) and bentonite (H-bent) was used as the carrier for encapsulating atrazine and imidacloprid to control their release in water and retard their leaching in soil. Strong interactions between CM-chit and H-bent in the composite were confirmed by FT-IR, and good dispersion of pesticides in the carrier was observed by SEM. According to the results of release experiments in water, the CM-chit/H-bent composite carrier showed double advantages of both encapsulation by the polymer and sorption by the bentonite. The time taken for 50 % of active ingredients to be released, t ₅₀, was prolonged to 572 h for atrazine and 24 h for imidacloprid, respectively. The difference between the two pesticides on release behavior was related to their hydrophobicity and water solubility. Leaching experiments through a soil layer showed that this novel carrier reduced the amount of pesticides available for leaching, and would be useful for diminishing the environmental pollution of pesticides.     

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。     

Application of encapsulation (pH-sensitive polymer and phosphate buffer macrocapsules): a novel approach to remediation of acidic ground water

Macrocapsules, composed of a pH-sensitive polymer and phosphate buffer, offer a novel remediation alternative for acidic ground waters. To test their potential effectiveness, laboratory experiments were carried out followed by a field trial within a coal pile runoff (CPR) acidic contaminant plume. Results of traditional limestone and macrocapsule treatments were compared in both laboratory and field experiments. Macrocapsules were more effective than limestone as a passive treatment for raising pH in well water from 2.5 to 6 in both laboratory and field experiments. The limestone treatments had limited impact on pH, only increasing pH as high as 3.3, and armoring by iron was evident in the field trial. Aluminum, iron and sulfate concentrations remained relatively constant throughout the experiments, but phosphate increased (0.15-32 mg/L), indicating macrocapsule release. This research confirmed that macrocapsules may be an effective alternative to limestone to treat highly acidic ground water.     

管道特征对给水管网中锰释放的影响

针对南方某市历年来与锰相关的多次黄水问题,在当地黄水多发区域挖取10年管龄的旧PE管和20年管龄的镀锌钢管,搭建中试装置,开展了管网中锰释放行为的中试研究,并以新PE管做对比,探讨了微生物对管网内锰的氧化沉积的影响。实验结果表明,在进水锰浓度很低时,镀锌钢管与旧PE管的管壁沉积物中均会出现锰的释放。镀锌钢管中释放的锰主要为溶解性锰,释放量大;而旧PE管中释放的锰主要为不溶态的锰,且释放量小。同时,镀锌钢管管道浸泡结果表明,随着余氯浓度的提高,镀锌钢管中溶解锰的释放会显著降低,但即使余氯浓度高达15 mg·L-1仍会有25.3 μg·L-1的溶解锰的释放。新旧PE管的对比实验表明,当提高进水Mn（Ⅱ）浓度时,旧PE管中Mn（Ⅱ）在6.67 h内的氧化量低于新PE管,这可能是旧PE管生物膜中的锰还原菌含量较多导致的。     

Rice and wheat straw ashes: Characterization and modeling of pretilachlor sorption kinetics and adsorption isotherm

The rice straw ash (RSA) and wheat straw ash (WSA) were explored as low cost adsorbent for pretilachlor removal from water. The ashes were characterized and sorption behavior of pretilachlor was evaluated. Kinetics study suggested that the modified Elovich model best explained the pretilachlor sorption on both the ashes. The adsorption data were analyzed using 2-, 3- and 4-parameter models and nine error functions were used to compute the best fit isotherm by nonlinear regression analysis. The pretilachlor was more sorbed onto the RSA (22.0–92.2%) than the WSA (11.4–61.4%) and percent adsorption decreased with increase in the herbicide concentration in solution. Isotherm model optimization analysis suggested that the Freundlich and the Temkin isotherms were the best models to predict the pretilachlor adsorption onto the RSA and the WSA. The error analysis suggested that the reciprocal of the observed squared (ROS) and the reciprocal of the predicted squared (RPS) error functions provided the best determination of the adsorption constants for the Freundlich and the Temkin isotherms, respectively. The RSA, which exhibited higher pretilachlor sorption potential, can be utilized as low cost adsorbent for pesticide removal from contaminated water.     

Sorption and leaching of flucetosulfuron in soil

Abstract

The adsorption–desorption and leaching of flucetosulfuron, a sulfonylurea herbicide, was investigated in three Indian soils. Freundlich adsorption isotherm described the sorption mechanism of herbicide with adsorption coefficients (K_f) ranging from 17.13 to 27.99 and followed the order: Clayey loam?>?Loam?>?Sandy loam. The K_f showed positive correlation with organic carbon (OC) (r?=?0.910) and clay content (r?=?0.746); but, negative correlation with soil pH (r = ?0.635). The adsorption isotherms were S-type suggesting that herbicide adsorption was concentration dependent and increased with increase in concentration. Desorption followed the sequence: sandy loam?>?clayey loam?>?loam . Hysteresis (H) was observed in all the three soils with H?<?1. Leaching of flucetosulfuron correlated positively with the soil pH; but, negatively with the OC content. Sandy loam soil (OC- 0.40%, pH ?7.25) registered lowest adsorption and highest leaching of flucetosulfuron while lowest leaching was found in the loam soil (pH ? 7.89, OC ? 0.65%). The leaching losses of herbicide increased with increase in the rainfall intensity. This study suggested that the soil OC content, pH and clay content played important roles in deciding the adsorption–desorption and leaching behavior of flucetosulfuron in soils.     

土工管袋法固结底泥氮磷转化特征及释放风险

以土工管袋法脱水固结底泥为对象,对巢湖清淤底泥固结前后管袋内底泥氮磷形态以及释放特征进行分析,研究土工管袋固结法对疏浚底泥氮磷转化影响及释放风险。结果表明,与湖体原泥相比,固结后底泥有机质和总氮均出现下降趋势(有机质下降10.87%,总氮含量下降3.50%),但总磷明显升高(增幅约18.89%)。同时,固结后底泥最大吸附量(Q_m)较未固结底泥增幅约1.35倍,为0.89 mg·g⁻¹。固结后底泥等温平衡浓度(EPC₀)较固结前底泥降低约1.58倍,这表明疏浚底泥固结后磷释放风险降低。氮磷形态分析结果表明,管袋固结后氨氮含量降低,但硝氮的质量浓度没有明显变化。固结后底泥中铁结合态磷、铝结合态磷较未固结底泥分别增加约1.20、1.49倍,有机磷含量则较固结前底泥下降约71.6%。静态释放结果表明,固结底泥氮释放随温度增加而增加,其中30 ℃条件下固结底泥氨氮释放速率为3.31mg·(m²·d)⁻¹,约是湖体未固结底泥10%。但固结底泥磷处于吸收状态,其中30 ℃条件下磷酸根吸收速率最大为2.74 mg·(m²·d)⁻¹。以上结果表明,固结底泥氮磷总量、活性态及其释放通量均降低,再次释放风险较小。     

土壤中咪唑啉酮类除草剂的分析及归趋研究

咪唑啉酮类除草剂具有较长的残留活性,研究其在土壤中的环境行为具有重要的意义.介绍了咪唑啉酮类除草剂的特性,评述了咪唑啉酮类除草剂在土壤中的前处理方法和分析方法以及该类除草剂在土壤中的吸附、降解和迁移特性,并针对目前的状况和存在的问题提出了今后的研究方向.