Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.     

Adsorption of Atrazine and Alachlor to Aquifer Material and Soil

Atrazine [6-chloro-N-ethyl-N′-(1-methyl)-1,3,5 triazine-2,3-diamine] and alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide] are agricultural herbicides used in large quantities and, as a consequence, are common contaminants in groundwater and surface water. The retention of these herbicides in soils and their degradation in aqueous environments is highly dependent upon their adsorption to solid surfaces. The adsorption of atrazine and alachlor was investigated on three typical Kansas and underlying aquifers known to be vulnerable to contamination. More alachlor was adsorbed to the soils and sediments than atrazine. The adsorption coefficients for atrazine were 2 to 5 times higher for soils than for aquifer sediments. For alachlor, the adsorption coefficients were 4 to 20 times higher for soil than for aquifer solids. Both linear and Freundlich isotherms represented the adsorption data well in all cases. The slope of the Freundlich isotherms, 1/n, was close to one, with the exception of alachlor adsorption onto the Topeka aquifer sediment (1/n = 0.67). The K _d values found in these studies were comparable to the lower range of those reported in the literature.     

轮作水稻对大棚土壤硝化作用和氮挥发的影响

通过大棚茄子—水稻轮作(GER)和大棚茄子—揭膜休闲(GEF)2种栽培模式在大棚茄子栽培期间土壤硝化作用强度、氨挥发速率和土壤水热条件指标动态变化的比较,研究了轮作水稻对大棚土壤硝化作用和氨挥发的影响。结果表明:(1)GER模式在大棚茄子各生育期土壤硝化作用强度都显著高于GEF土壤,苗期最高峰时表土和根际土硝化作用强度分别为56.6,101.4mg/(kg·h),比GEF模式增加了34.8%和42.4%;(2)GER模式在大棚茄子基肥和追肥施用后土壤氨挥发速率都显著低于GEF土壤,累积氨挥发量为1.21kg/hm~2,比GEF模式减少了76.7%;(3)GER模式在大棚茄子各生育期表土和根际土NH4+—N含量都低于GEF土壤,NO3-—N含量高于GEF模式;(4)GER和GEF模式在大棚茄子收获后表土NH4+—N含量分别为30.4,45.9mg/kg,NO3-—N含量分别为265.4,255.5mg/kg,存在明显的氮素累积。夏季轮作水稻缓解了大棚土壤酸化、提高了大棚茄子生长期间土壤pH、温度和含水量,对大棚土壤硝化作用有明显的促进作用,可减少土壤氨挥发损失。但硝化作用强度的增加促进了土壤中硝酸根的累积,存在加剧土壤次生盐渍化和氮损失的风险,应加强轮作周期氮肥合理施用技术研究。     

太湖地区大棚菜地土壤养分与地下水水质调查

为了解和评价太湖地区大棚菜地土壤肥力及其周边地下水硝酸盐和氨氮含量状况,以直湖港小流域为研究区域,采集大棚和露天菜地土样192和54个,浅层地下水样26和10个,分析土壤速效养分、全氮和有机质含量,土壤pH和EC值,地下水硝酸盐和氨氮含量。结果表明,直湖港小流域大棚菜地耕层土壤速效氮含量为279 mg/kg,是露天菜地的2.6倍。大棚菜地耕层土壤速效磷、钾含量分别为188 mg/kg和203 mg/kg,与露天菜地无显著差异。大棚菜地耕层土壤速效氮磷钾含量均高于全国第二次土壤普查分级的最高标准,且氮磷钾养分表聚严重。耕层土壤有机质含量偏低为13/kg;大棚菜地耕层土壤pH值为5.6呈弱酸性,37%的该区大棚菜地种植面积土壤pH值低于作物生理障碍的临界值,该区16.4%的大棚蔬菜种植面积土壤EC值超过作物生育障碍临界值。参照我国生活饮用水卫生标准评价,结果表明,直湖港小流域大棚菜地周边浅层地下水硝酸盐超标率为35%,氨氮超标率为8%。     

Valorization of Organic Wastes to Reduce the Movement of Priority Substances Through a Semiarid Soil

In this work, we examined the effect of two different organic wastes, composted sheep manure and coir, on the sorption, persistence, and mobility of three pesticides (alachlor, chlorfenvinphos, and chlorpyrifos) included as priority substances in European Directive 2013/39/EU. With this aim, leaching studies were conducted using disturbed soil columns filled with a typical agricultural soil (hipercalcic calcisol) from a semiarid area (southeastern Spain) to determine their potential for groundwater pollution. The three compounds were found in leachates of unamended soil although in different proportions: 53% (alachlor), 9% (chlorfenvinphos), and 6% (chlorpiryfos). The addition of organic wastes significantly increased the sorption of the studied pesticides. As a consequence, the half-lives of the studied pesticides were higher in amended than in unamended soils. A marked reduction of the amount recovered in leachates was observed in the amended soils, except for chlorpiryfos, whose recoveries barely changed. According to their potential groundwater pollution calculated as the groundwater ubiquity score (GUS) index, alachlor and chlorfenvinphos show medium leachability while chlorpiryfos is unlikely to leach.     

Polymeric microcapsules of alachlor and metolachlor: preparation and evaluation of controlled-release properties.

The microencapsulation of alachlor and metolachlor in the polymers cellulose acetate butyrate, ethyl cellulose, poly(methyl methacrylate), and poly(alpha-methylstyrene) with different emulsifiers is described. The controlled-release properties of these formulations were measured under greenhouse conditions on barnyardgrass, crowfootgrass, smallflower morningglory, and Palmer amaranth. The emulsifiers had little effect on the activity of the herbicides. The herbicidal activities of the poly(methyl methacrylate) and poly(alpha-methylstyrene) formulations were consistently lower on all weed species when compared to the activities of the cellulose acetate butyrate, ethyl cellulose, and commercial formulations. The ethyl cellulose formulation of alachlor exhibited controlled-release properties. The results with metolachlor were similar to those with alachlor except that none of the metolachlor formulations exhibited efficacy superior to that of the commercial formulation or controlled release properties.     

滴灌施肥对设施番茄产量和氮素表观平衡的影响

针对设施蔬菜传统栽培管理模式中水肥过量使用,导致水资源浪费、硝态氮淋失污染地下水、病虫害增加等问题,以山东省寿光市一年两季设施番茄传统灌溉施肥模式为对照,通过测定番茄产量和土壤硝态氮累积量以及经济和环境效益分析,研究了滴灌施肥一体化栽培管理模式对设施番茄产量和氮素表观平衡的影响。结果表明,与传统水肥管理模式相比,滴灌施肥一体化模式显著提高了番茄产量,全年增产19.6%,净收益提高33%;氮肥和灌溉用水量分别减少了80%和36%。传统水肥管理模式090 cm土层NO3- -N平均残留量和表观氮素盈余分别高达N 107551和99961 kg /hm2,而滴灌施肥一体化模式则分别为N 57246和-4640 kg/hm2,大大降低了氮素淋洗和气态损失的潜在风险。     

蔬菜大棚种植区土壤与地下水中典型有机污染物健康风险评价

在对石家庄某蔬菜大棚种植区进行采样测试分析的基础上,针对其表层土壤及地下水有机污染特征,依托美国环保局(U.S.EPA)所提健康风险评价四步法,以菜农为敏感人群,尝试开展蔬菜大棚种植区的健康风险评价工作。在评价过程中,主要考虑经口摄入土壤和饮用地下水两种暴露途径,而鉴于蔬菜大棚内表层土壤与大棚周围表层土壤中污染物种类和含量存在明显差异这一事实,又将经口摄入土壤途径细分为经口摄入大棚内表层土壤和经口摄入大棚外表层土壤。评价结果显示,菜农的非致癌风险和致癌风险目前均处于可接受风险水平;邻苯二甲酸二正丁酯是最主要的非致癌污染物,其非致癌风险贡献率高达84.2%,狄氏剂是最主要的致癌污染物,其致癌风险贡献率为51.35%;饮用地下水途径是最主要的非致癌风险贡献途径,其非致癌风险贡献率高达94.42%;经口摄入棚外表层土壤途径是最主要的致癌风险贡献途径,其致癌风险贡献率为47.14%。     

Environmentally friendly formulations of alachlor and atrazine: preparation, characterization, and reduced leaching

Atrazine and alachlor formulations were designed by encapsulating the herbicide molecules into phosphatidylcholine (PC) vesicles, which subsequently were adsorbed on montmorillonite. PC and montmorillonite are classified as substances of minimal toxicological risk by the U.S. EPA. PC enhanced alachlor and atrazine solubilities by 15- and 18-fold, respectively. A 6 mM PC:5 g/L clay ratio was found as optimal for PC adsorption on the clay. Active ingredient contents of the PC-clay formulations ranged up to 8.6% for atrazine and 39.5% for alachlor. Infrared spectroscopy showed hydrophobic interactions of herbicide molecules with the alkyl chains of PC, in addition to hydrophilic interactions with the PC headgroup. Release experiments in a sandy soil showed a slower rate from the PC-clay formulations than the commercial ones. Soil column experiments under moderate irrigation and bioactivity experiments indicate that a reduction in the recommended dose of alachlor and atrazine can be accomplished by using PC-clay formulations.     

Development of formulations to improve the controlled-release of linalool to be applied as an insecticide

In recent studies, insecticide activity of a monoterpene, linalool, has been demonstrated, finding, however, limitations in application because of its rapid volatilization. Potential effectiveness of microcapsules and effects of various types of matrices on its stability as controlled-release systems for the slow volatilization of linalool to be applied as insecticide were evaluated. To study controlled-release, linalool was entrapped into microcapsules, inclusion complexes, and beads, obtained by different methods, inverse gelation (IG1, IG2, IG3, IG4, and IG5), oil-emulsion-entrapment (OEE), interfacial coacervation (INCO), and chemical precipitation (Cyc5 and Cyc10). The encapsulation yield turned out to be different for each formulation, reaching the maximum retention for IG1 and OEE. In controlled-release, OEE followed by INCO presented a long time necessary for releasing as a result of the presence of glycerol or chitosan. These results pointed out remarkable differences in the release behavior of linalool depending on matrix composition and the method of encapsulation.     

农药在土壤中迁移的区域差异研究

建立了一个基于三种农药在土壤中根区和中间渗流区迁移能力的模型,并采用不同类型土壤分布区域的土壤理化性质,区域气候与水文特以及农药理化性质等参数,进行了农药对区域地下水潜在污染能力的评价。     

氯丹和灭蚁灵在典型污染场地的空间分布研究

测定分析了典型氯丹和灭蚁灵污染场地上的土壤、浅层地下水、地表水和底泥样品,应用地统计学的理论和方法研究了氯丹和灭蚁灵的空间结构与分布特征。结果表明,氯丹、灭蚁灵空间变异性高,随机因素对空间变异起主导作用。厂区内生产车间附近土壤中氯丹和灭蚁灵污染严重,存在明显的水平迁移,污染扩散范围与风向呈现一定相关性。氯丹和灭蚁灵随水的淋溶作用存在显著的竖直迁移,已经扩散至深层土壤中。污染场地附近的浅层地下水和地表水均被污染,底泥污染被限制在排污口附近。通过Kriging法插值画出土壤和浅层地下水中氯丹和灭蚁灵的等值线图,清晰地看出氯丹和灭蚁灵的分布趋势:氯丹和灭蚁灵在表层土壤中污染程度较重,下层土壤和浅层地下水中的污染分布均与上层相对应。土壤、浅层地下水、地表水和底泥中灭蚁灵浓度均小于氯丹,这与氯丹和灭蚁灵的挥发性、迁移性、吸附性等理化性质有关。通过与同类POPs污染场地研究的对比分析发现,此类场地土壤中的POPs分布存在共性特征。     

寿光大棚菜地土壤呼吸强度、酶活性、pH与EC的变化研究

为防治土壤退化、促进农业可持续发展提供科学依据,以寿光地区露地土壤作对照,研究了连作1、5、8和12年大棚蔬菜(番茄)土壤有关生物学指标的变化。结果表明,土壤呼吸强度和脱氢酶活性棚内高于棚外,并随连作年限延长开始增强而后减弱,由于管理差异,12年棚龄土壤又回升。随着连作年限延长,土壤脲酶活性逐渐减弱,而过氧化氢酶活性逐渐增强;土壤呼吸强度和酶活性都由表层向底层逐渐减弱。土壤pH随连作年限增加逐渐下降,而EC逐渐增加,至12年棚龄时,与对照比0—20 cm土层pH下降了1.06单位,其他层次变化不显著。试验还表明,该地区表层土壤pH变化于6.45~7.51,EC 0.5 mS/cm,能较好地满足作物生长需要,同时,EC是影响土壤pH及酶活性变化的重要因素。土壤EC及过氧化氢酶活性可作为反映大棚菜地土壤质量变化的参考指标。     

An Empirical Model for Estimating Remediation Costs at Contaminated Sites

A model for estimating the remediation costs at contaminated sites is developed, in which the predictor variable is a composite of surface, subsurface, and contaminant risk factors. Calibration of the model is performed at 83 sites in an urbanized watershed with diverse surface geology in southeastern Michigan. These test sites exhibited different extents of contamination, including some where only soil was contaminated, and others where soil and groundwater were contaminated. The model was then applied to 79 sites with multiple contamination extents within different watersheds in North America, Europe, Australia, and Africa. The results indicate a very high correlation between the estimated and actual remediation costs at these sites. This model thus has the potential for providing reliable estimates of remediation costs across a broad array of soil and groundwater contamination scenarios, including dense nonaqueous phase liquid (DNAPL) contamination in sandy soil and lead in clay soil.     

不同水氮条件对日光温室冬春茬黄瓜栽培氨挥发的影响

通过设置不同灌水、施氮处理,采用通气法研究了温室土壤施肥带与非施肥带的氨挥发特征,探讨了节水灌溉、减量施氮处理与传统水氮处理土壤氨挥发的差异及其影响因素。结果表明,冬春季温室黄瓜土壤在氮肥基施7 d后出现氨挥发峰值,减施氮25%处理的氨挥发峰值比传统施氮处理降低18.2%~34.3%;追肥后,施肥带和非施肥带的氨挥发速率峰值分别在第1 d和第5 d出现,减施氮25%处理与传统施氮处理相比,氨挥发速率峰值降低12.3%~37.2%;节水灌溉处理与传统灌水处理相比,氨挥发峰值则提高3.9%~47.0%。土壤中铵态氮含量以及温度的升高可促进土壤的氨挥发,而土壤含水量则与氨挥发速率呈负相关。在黄瓜花期和初瓜期,施肥带的累计氨挥发量显著高于非施肥带,而初瓜期之后,施肥带与非施肥带的氨挥发无显著差异。整个黄瓜生育季的累计氨挥发量为11.4~26.6 kg.hm 2;与传统施氮和灌水处理相比,减施氮25%处理的累计氨挥发量可降低20.8%~22.2%,但节水灌溉处理的累计氨挥发量却有所增加,增加幅度为0~4.51%。适宜减少灌水和氮肥用量不会降低黄瓜产量,且可大幅度提高灌水和氮肥利用效率。     

亚洲土壤和地下水金属污染风险评价---综述近期研究趋势以及现有环境法律法规

Asia is experiencing a more rapid economic growth compared to any other regions. The contamination of soil and groundwater with metals can mainly be attributed to human activities; therefore, risk assessments to characterize the nature and magnitude of risks to humans and ecological receptors from contaminants are important. Risk assessments are often iterative processes, which involve identification and filling data gap. Experimental samplings, geostatistical and multivariate statistical methods as well as multimedia risk assessment modeling are the three major methodologies used in the assessment of metal contamination in soil and groundwater. This review highlights a number of measurements for improving risk calculation methods and expounds scientific approaches that involve the identification of the major source of contamination, exposure pathways and bioavailability of metals. In general, risk assessments of metals in soil and groundwater worldwide are mainly focused on the levels of contamination, identification of exposure pathways, and prediction of the probability of contamination. To date, very limited studies have reported the development of relevant environmental laws and policies in the regulation of soil and groundwater contamination in Asia. The development, variations and limitations in the regulations of soil and groundwater contamination among developed countries may provide helpful guidance for the developing countries in Asia.     

Ammonia Volatilization from Soil,Dry-Matter Yield,and Nitrogen Levels of Italian Ryegrass

Nitrogen (N) loss by ammonia (NH₃) volatilization is the main factor for poor efficiency of urea fertilizer applied to the soil surface. Losses can be suppressed by addition of zeolite minerals to urea fertilizer. The objective of this study was to evaluate ammonia volatilization from soil and dry-matter yield and nitrogen levels of Italian ryegrass. A greenhouse experiment was carried out with the treatments of urea, urea incorporated into soil, urea + urease inhibitor, urea + zeolite, ammonium nitrate, and unfertilized treatment. Ammonia was captured by a foam absorber with a polytetrafluoroethylene tape. There were few differences between zeolite and urease inhibitor amendments concerning NH₃ volatilization from urea. Results indicate that zeolite minerals have the potential to improve the N-use efficiency and contributed to increasing N uptake. Zeolite and urea mixture reduced 50% the losses by volatilization observed with urea.     

控释尿素减少双季稻田氨挥发的主要机理和适宜用量

【目的】研究施用控释尿素减少稻田氨挥发的主要机理,及有效减少氨挥发的施用量,为充分发挥控释尿素的环保效应提供参考。【方法】盆栽试验于2017年在湖南农业大学试验基地大棚内进行,供试土壤为潮砂泥田水稻土,供试早稻、晚稻品种为中早39和泰优390,供试控释氮肥为树脂包膜控释尿素。设置不施氮肥 (CK)、普通尿素 (U) 以及控释尿素等氮量 (CRU1)、减氮10%(CRU2)、减氮20%(CRU3) 和减氮 30% (CRU4) 6个处理。采用密闭室间歇通气法监测双季稻田氨挥发特征,监测同期田面水铵态氮 (NH₄+-N) 和硝态氮 (NO₃–-N) 浓度、pH值及土壤温度动态变化。【结果】施用控释尿素 (CRU) 显著降低了稻田氨挥发损失,各施氮处理稻季氨挥发累积损失量表现为U > CRU1 > CRU2 > CRU4≈CRU3。与U处理相比,CRU处理明显降低了氨挥发速率峰值,且不同程度减少了稻田氨挥发累积损失量,减排程度可达50.3%～70.1%。CRU处理氨挥发损失率为5.6%～8.13%,且早、晚稻均以CRU3和CRU4处理较低。与U处理相比,早、晚稻CRU处理施基肥后田面水中的铵态氮浓度峰值分别降低74.5%～80.4%、53.4%～76.0%,施分蘖肥后分别降低69.5%～89.1%、67.3%～80.3%。U、CRU1、CRU2、CRU3和 CRU4 处理早稻田面水平均 pH 值分别为7.26、7.22、7.25、7.32和7.14,各处理差异不显著;晚稻田面水平均pH值分别为7.85、7.71、7.72、7.72和7.66,CRU处理均显著低于U处理。U处理氨挥发速率和田面水铵态氮浓度呈极显著正相关 (r = 0.8813),与硝态氮浓度呈显著负相关 (r = –0.5319);CRU处理与U处理变化规律类似,CRU3和CRU4处理氨挥发速率与田面水铵态氮浓度达到显著正相关 (r = 0.5388和0.4245),各处理氨挥发速率与田面水pH值和10 cm土层温度相关不明显。【结论】施用控释尿素可显著降低稻田水面中的铵态氮含量,减少由于施肥导致的pH值增加,因而显著降低了稻田的氨挥发损失量,减少了氨挥发损失率。早稻和晚稻均以控释尿素施用量减少20%～30%的氨挥发减排效果最为明显。     

水氮调控对设施土壤氨挥发特征的影响

基于连续6年设施番茄水氮调控定位试验,采用高分辨激光光谱法观测分析灌水下限(土壤水吸力为W_1:25 kPa、W_2:35 kPa、W_3:45 kPa)和施氮量(N_1:75 kg N/hm~2、N_2:300 kg N/hm~2、N_3:525 kg N/hm~2)对设施土壤氨挥发通量、累积挥发量、番茄产量及单产累积排放量的影响。结果表明:灌水下限、施氮量及两者交互作用极显著的影响设施土壤氨挥发通量峰值、累积挥发量、单产氨挥发累积量、氨挥发损失率和番茄产量。氨挥发通量表现为施氮后6～8天氨挥发达到峰值。经验S模型可以较好地表征基肥和追肥2个时期氨挥发累积量随时间的变化,氨挥发特征参数表现为基肥期以灌水下限和水氮交互影响为主,追肥期以施氮量和水氮交互影响为主。与基肥相比,采用滴灌追肥可显著的降低氨挥发累积量94.78%～96.30%。受土壤pH和土壤NH_4~+-N含量及施肥带比例影响,氨挥发的氮损失率在0～2%。施氮量为300 kg N/hm~2和灌水下限25 kPa组合的水氮处理(W_1N_2)是协调氨挥发量和设施番茄产量的最佳水氮管理模式。     

Norflurazon mobility, dissipation, activity, and persistence in a sandy soil as influenced by formulation

Five ethylcellulose (EC) microencapsulated formulations (MEFs) of norflurazon were prepared and applied in soil to study their mobility, dissipation, activity, and persistence. The results show that the release into water of norflurazon from EC microspheres was retarded when compared with that of commercial herbicide. The mobility of norflurazon from MEFs into soil columns has been greatly diminished in comparison with that of its current commercial formulation (CF). Norflurazon distribution at different depths in the soil was higher in the upper ring (up to 50% of the initial application). In contrast, the residues from commercial norflurazon along the complete soil column were only about 2%. Degradation and bioassay experiments showed that the MEFs had greater persistence (t1/2 values were 7.72 and 30.83 weeks for CF and MEFs, respectively) and herbicidal activity than the commercial formulation. The use of these formulations can be advantageous, because they can minimize the risk of groundwater contamination and permit herbicide use at reduced rates, maintaining the desired concentrations of herbicide in the topsoil layer for longer periods of weed control.