两种环境激素类农药及其混合剂在土壤中的降解研究

为了深入了解环境激素类农药在与其它多种农药同时存在条件下在土壤中的降解过程、阐释其机理,用室内培养的方法,研究氯氰菊酯、毒死蜱两种农药及其混合剂在灭菌和未灭菌土壤中的降解特征。结果表明,两种农药及其混合剂在土壤中的降解是微生物主导的过程;灭菌土壤中,混合剂中各农药组分与其单独存在降解过程基本一致,均符合单室模型C=C0e-kt,降解半衰期也与其单独存在相近;但在未灭菌土壤中,混合剂中各农药组分降解特点与其单独存在有所不同。两种农药单独存在时,氯氰菊酯、毒死蜱在未灭菌土壤中的降解方程均符合单室模型,降解半衰期分别为31.5 d和57.8 d;混合剂中各组分农药在未灭菌土壤中的降解过程符合双室模型C=C1e-αt+C2e-βt,不同阶段降解半衰期不同,氯氰菊酯前期和后期半衰期分别为33.0 d和53.3;而毒死蜱前期和后期的半衰期则分别为63.0 d和86.6 d。在未灭菌土壤中多种农药存在时各种农药降解均呈现先快后慢的特点。     

有机磷农药氧化乐果在土壤中降解规律的试验研究

采用大田、盆栽及室内培养试验，研究了氧化乐果在兰州地区蔬菜土壤中的残留和降解并研究了土壤微生物、光照、有机肥含量对其降解的影响，比较了不同土壤中氧化乐果的降解速率。结果表明，微生物寻氧化乐果的降解作用影响较大，光照的影响次之，土壤有机质的增加对其降解有促进作用，在耕种灌淤土中的降解速率大于自然灰钙土。田间试验得出氧化乐果在自然条件下降解的半衰期2－3d，需17d就可基本降解完毕。     

水稻土中广灭灵残留动态及降解影响因子的研究

对水稻土中广灭灵残留消解动态及降解影响因子研究结果表明 ,广灭灵在 4种水稻土中降解符合 1级动力学方程C =C0 e-kt,其降解半衰期为 5 7～ 2 2 0d。广灭灵降解以微生物降解为主 ,土壤灭菌处理大大降低广灭灵降解速率 ,土壤理化性质、温度、湿度、pH值是影响广灭灵降解的重要因素。广灭灵降解速率与不同类型水稻土有机质含量呈显著负相关关系 ,相关系数为 - 0 8336。随温度上升而广灭灵降解有加速趋势 ,但常温 2 5℃时广灭灵降解速率高于 35℃处理 ,增加土壤湿度及施用石灰增加土壤 pH值均加快广灭灵降解速率     

双草醚在稻田土壤中的降解及其影响因子的研究

采用了实验室模拟方法研究了双草醚在不同土壤中的降解动态。结果表明,在未灭菌的土壤中,双草醚三种浓度(2.0、10.0、50.0mg kg-1)处理的半衰期为7.6~10.3d,远远小于在灭菌土壤中3种添加浓度处理的半衰期(43.3~61.9 d);双草醚在偏酸土壤中降解较快,随着土壤含水量的增加和环境温度的增高,双草醚降解速度加快。4种试验因子中土壤微生物是影响双草醚降解的主要因素,有利于土壤中微生物生长的环境因素,如偏酸的土壤、较高的温度和土壤湿度等,也能促进土壤中双草醚的降解。     

丙硫克百威在几种土壤中的迁移和降解研究

对丙硫克百威在湖南几种土壤中的迁移和降解进行了研究。结果表明 :丙硫克百威在土壤中能被雨水淋溶迁移 ,在 2 0cm耕作土层中 ,丙硫克百威及其降解产物克百威要分布在 0～ 1 4cm范围内 ,丙硫克百威的使用 ,对地下水污染的可能性比较小。丙硫克百威在第四纪红土红壤、河潮土、河潮泥中半衰期分别为 6.3d、7.3d、8.8d。在施药 3 0d内 ,丙硫克百威在土壤中降解很快 ,化学降解作用要大于生物降解作用 ,其中部分降解产物为克百威、3 -羟基克百威 ,其中 3 -羟基克百威在丙硫克百威降解过程中产生甚微。克百威的继续降解随时间无明显的规律。     

土壤中双氰胺降解及与降解菌的关系

采用灭菌土培、非灭菌土培、田间蔬菜种植、添加外源降解菌土培试验研究了土壤中双氰胺（DCD）降解及与降解菌的关系。结果显示,不论是单施DCD、尿素配施DCD,还是碳酸氢铵配施DCD的土壤,灭菌处理的土壤中DCD半衰期分别比不灭菌处理的长13.56、5.79、14.51d。降解菌生长期间,降解菌总量（x）与DCD降解呈显著正相关,拟合的线性方程为y=3.1841x-2.5452,r=0.9752。外源DCD降解真菌可在灭菌土壤中定殖并有效降解DCD,培养15d后,U＋DCD＋DCD降解菌处理土壤中DCD降解真菌的数量增加至36.40×105cfu,且DCD含量极显著降低。这些结果表明土壤中DCD降解与降解菌关系极为密切,添加外源真菌加速了土壤中DCD降解。     

适宜水分和养分提高土壤中磺酸二甲嘧啶降解率

医疗和养殖过程中抗生素的广泛使用导致了土壤环境中抗生素的污染。为了解进入农田土壤中抗生素的降解规律,该文以养殖业广泛使用的磺胺二甲嘧啶和2种不同养分水平的土壤为试验材料,采用盆栽方法研究了肥料种类(有机肥、NPK肥、N肥、PK肥等)、耕作强度(翻耕、免耕)、水分条件(长期干燥、长期湿润、干湿交替、长期潮湿)及种植作物(种植蔬菜、不种蔬菜)对土壤中磺胺二甲嘧啶降解的影响。结果表明,与不施肥处理比较,施用有机肥、NPK肥、N肥可促进土壤中磺胺二甲嘧啶在土壤中的降解,并以施用有机肥的效果最为明显;但施用PK肥对土壤中磺胺二甲嘧啶的降解影响不明显。翻耕可促进土壤中磺胺二甲嘧啶的降解,干湿交替、长期湿润比长期干燥和长期潮湿土壤环境下更有利于磺胺二甲嘧啶的降解。种植蔬菜比不种蔬菜土壤的磺胺二甲嘧啶的降解率高,根际土壤中磺胺二甲嘧啶的降解高于总体土壤。高养分土壤中磺胺二甲嘧啶的降解一般高于低养分土壤。分析认为,施肥、土壤养分水平、种植蔬菜对土壤中磺胺二甲嘧啶的降解的影响可能主要与这些因素改变了土壤微生物活性有关;翻耕可促进土壤中抗生素的光降解强度。研究认为,施肥、耕作和水分管理可以在一定程度上加速土壤中磺胺二甲嘧啶的降解。     

2-羟基-1,4-萘醌在土壤中降解作用和淋溶行为研究

采用室内培养法和土柱法,研究了2-羟基-1,4-萘醌在土壤中的降解作用和淋溶行为。结果表明,2-羟基-1,4-萘醌在灭菌和非灭菌土壤中的降解半衰期分别为3.47～6.98d和0.42～0.53d,且随着2-羟基-1,4-萘醌浓度增加,其降解半衰期延长。说明微生物对其降解过程起主导作用。参考POPs国际公约关于化学品持久性的定义,2-羟基-1,4-萘醌在土壤中属于易降解有机物。通过2-羟基-1,4-萘醌在土壤中的淋溶研究发现：当其添加浓度为5mg·kg-1和10mg·kg-1时,各处理土层中均未检出2-羟基-1,4-萘醌;当添加浓度为20mg·kg-1时,仅在0～10cm土层样品中检测到2-羟基-1,4-萘醌。与未老化土壤相比,2-羟基-1,4-萘醌在老化土壤中的淋溶作用减弱。     

土霉素在鸡粪中的残留及降解规律研究

检测了健康肉鸡以不同剂量土霉素混饲给药后,在不同时间鸡粪中土霉素的含量变化,并比较避光及人工光照条件下灭菌鸡粪中土霉素的降解规律,以及在避光条件下灭菌、未灭菌及灭菌后加降解菌处理,鸡粪中土霉素的降解规律。结果表明,健康肉鸡混饲给予土霉素（100、200、400mg·kg-1）后,鸡粪中土霉素排泄量在给药后6～8h达到高峰,峰浓度分别为13.58、36.15mg·kg-1和50.73mg·kg-1,并于30、62h和72h时检测不到土霉素;对鸡粪中土霉素的浓度随时间变化趋势进行曲线拟合,发现各处理组的这种变化趋势均符合一级动力学方程Ct=C0e-kt。经灭菌鸡粪中土霉素的降解受光照条件和土霉素初始浓度的影响,初始浓度为10、20、40mg·kg-1时,避光条件下,土霉素降解半衰期分别为55.5、123.8d和173.3d;人工光照条件下,鸡粪中的土霉素降解较快,降解半衰期分别为14.8、21.1d和27.5d。此外,无论是在避光还是人工光照条件下,较高初始浓度组的土霉素降解速率均比较低初始浓度组慢。去除光照因素后,鸡粪中所含土霉素的降解主要受微生物及土霉素初始浓度的影响,初始浓度为10、20、40mg·kg-1时,灭菌组土霉素降解半衰期分别为78.7、103.4d和157.5d,未灭菌组为40.5、50.6d和97.6d,灭菌后加降解菌组为14.5、33.6d和51.3d,说明鸡粪中微生物的存在可加快土霉素的降解。相同处理条件下,土霉素的降解速率随药物初始浓度的升高而降低。     

DMPP对菜地土壤氮素淋失的影响研究

采用小粉土和青紫泥原状土柱种植青菜，研究了尿素添加DMPP（3．4-二甲基吡啶磷酸盐）硝化抑制剂对土壤氮素淋失的影响。结果表明．在60天内，与常规尿素相比，小粉土和青紫泥DMPP处理硝态氮的累积淋失量分别降低66．8％和69．4％，氨氮淋失量提高9．7％和6．7％，无机氮降低59．1％和63．0％；蔬菜收获后，土壤0～15cm层无机氮增高34．1％和28．2％，土壤中氮素纵向迁移降低。可见，DMPP抑制剂施入土壤具有显著的氨氧化抑制作用，延缓蔬菜地土壤氨氮向硝态氮的转化，减轻氮素向水体迁移的风险。使用硝化抑制剂DMPP，由于土壤对氨氮的强吸附特性．迁移总量低，不会对地下水造成污染的风险。     

生物质炭施用及老化对石灰性紫色土中磺胺类抗生素迁移特征的影响

以长江上游低山丘陵区广泛分布的石灰性紫色土旱地的耕作层土壤为对象,采用室内批量平衡吸附试验和填装土柱穿透试验,研究了施用1%生物质炭及3年老化作用对2种磺胺类抗生素(磺胺嘧啶和磺胺二甲基嘧啶)吸附和迁移特征的影响。结果表明,Freundlich方程能更好地拟合抗生素在土壤中的等温吸附曲线,施用生物质炭提高了土壤对抗生素的吸附能力,吸附常数KF值依次为:老化1%施炭土新鲜1%施炭土对照土;土柱出流液的磺胺嘧啶和磺胺二甲基嘧啶相对浓度峰值均表现为:老化1%施炭土新鲜1%施炭土对照土,说明生物质炭的添加能有效减少控制紫色土中抗生素的淋失迁移,以对磺胺二甲基嘧啶的阻控效果较好;生物质炭老化3 a后土壤对抗生素的吸附作用与阻控效果均有所提高,主要归因于土壤pH的提高。     

土壤中磺胺类抗生素的检测方法优化及残留、降解研究

优化了磺胺甲基嘧啶(SM1)、磺胺二甲嘧啶(SM2)、磺胺对甲氧嘧啶(SMT)、磺胺甲噁唑(SMZ)4种磺胺类抗生素的高效液相色谱(H PLC)检测方法,分析了广州市养殖场周边土壤中磺胺类抗生素的残留特征,并进行了2种磺胺类抗生素的土壤降解试验。结果表明,4种磺胺类抗生素分别在0.10~10μg ml-1范围内线性良好,相关系数R>0.99。确定了最佳提取液为甲醇:含EDTA的Mcllvain缓冲液=1∶1(V/V),4种磺胺类药物的检测限与回收率分别为2.9~4.7μg kg-1、83.6%～90.1%。广州市18个规模化养殖场周边土壤中磺胺类抗生素污染以SM2为主,含量为1.75μgkg-1,其它3种均未被检出。土壤中磺胺类抗生素的含量总体呈随培养时间而不断下降的趋势,SMZ的降解速率大于SM2。     

乙二胺四乙酸在重金属污染土壤修复过程的降解及残留

为分析乙二胺四乙酸(ethylenediaminetetraacetic acid,EDTA)在修复重金属污染土壤中的环境风险,通过田间调查和培养试验研究EDTA在不同重金属污染土壤中的降解及其残留。田间调查结果表明,乐昌试验田EDTA施用6 a后,表层土壤及深层土壤中均没有检出EDTA残留。佛冈试验田在施用EDTA4个月后,表层土壤EDTA残留量为0.039~0.056 mmol/kg,仅为施入量的2%~5%,施用1a后土壤中未检测到EDTA。翁源试验田在EDTA施用45 d后,表层土壤中EDTA残留量约为施用量的一半,1 a后残留量为施入量的2,6%,深层土壤监测到EDTA残留,但地下水中并没有检测到EDTA,另外地下水中重金属含量并没有升高。因此,深层土壤对离子态和螯合态重金属具有较强的固定能力,可保护地下水免遭重金属的污染。培养试验结果表明,EDTA在土壤中降解遵循一级动力学方程,EDTA在赤红壤、褐土和重金属污染土壤中的降解速率常数分别为4.6×10~(-3)、1.4×10~(-2)和5.8×10~(-3),其降解的半衰期分别为71、25和53 d。EDTA在土壤中降解半衰期与土壤有机质含量和土壤阳离子交换量(cation exchange capacity)之间表现较好的相关性。微生物对EDTA在土壤中的降解具有显著的影响。总之,EDTA可在土壤中降解,建议在中国重金属污染土壤修复过程中可采用EDTA强化修复技术,EDTA的环境风险是可控的。     

唑螨酯在土壤中的降解及淋溶特性

为研究唑螨酯在环境中的行为特性,采用室内模拟试验方法,研究了唑螨酯在土壤中的降解及淋溶特性,通过降解半衰期和比移值Rf来评价其在土壤环境中的安全性。结果表明:唑螨酯在3种土壤中的降解符合一级动力学方程,好气条件下,在黄壤、水稻土和石灰土的降解半衰期分别为81.5、96.3和84.5 d,唑螨酯在水稻土中较难降解,在黄壤和石灰土中中等降解;厌气条件下的半衰期分别为154.0、56.3和43.3 d,水稻土和石灰土中中等降解,黄壤中较难降解。唑螨酯在黄土、水稻土和石灰土中比移值Rf均为0.083,唑螨酯在3种土壤中均不移动,正常条件下不会对地下水造成污染。综上所述,唑螨酯在土壤环境中具有较强的稳定性,因此应严格掌握其使用量和使用时期,同时建议加强对唑螨酯残留的跟踪监测。     

Degradation and adsorption of fosthiazate in soil

Adsorption and degradation behavior of a pesticide in soil has a strong effect on its environmental fate as well as efficacy for pest control. Fosthiazate is an organophosphate compound that is currently under development as a nonfumigant nematicide. In this study, we evaluated adsorption and degradation kinetics of fosthiazate in three U.S. soils with different properties. Adsorption of fosthiazate in mineral soil was negligibly weak but appeared to increase with soil organic matter (OM) content. The half-life (T(1/2)) of fosthiazate ranged from 0.5 to 1.5 months in nonsterile soils but was prolonged to 1-3 months after sterilization. Degradation of fosthiazate in soil appeared to be caused by both chemical and microbial transformations. The persistence of fosthiazate generally decreased with increasing soil pH, but increased with increasing soil OM and clay contents. This results suggest that fosthiazate may have an enhanced leaching potential in acidic soils with low OM content, and its efficacy in high pH soils may not last as long as in neutral soils because of faster degradation.     

The Leaching Behavior of Aldicar Among Complex Pollution System Composed of Surfactant SDBS and Aldicarb

The leaching behavior of aldicarb among the complex pollutionsystem composed of aldicarb and surfactant – sodiumdodecylbenzenesulfonate (SDBS) was studied by soil column.Distilled water was used to simulate rain in order to obtain therainfall of 235 mm for each time. Three simulations were carriedout successively to give 705 mm rainfall in all. The results ofmulti-step leaching experiment showed that compared with controlcolumn, SDBS can increase the vertical distance of aldicarbmoving and accelerate the leaching. As the concentration of SDBSincreased from 250 to 500 mg kg^-1 of soil, not only theleaching depth of aldicarb increased by 20 cm, but also below10 cm depth in soil column the concentration of aldicarb at thesame depth increased obviously. This will enhance the danger ofgroundwater pollution. SDBS affected the leaching behaviour ofaldicarb in soil by influencing its water solubility, adsorptioncapacity and degradation process. The mechanism of this complexeffect has been discussed in this article.     

Laboratory studies on the leaching of aldicarb through a tropical soil from Belize,Central America

Studies in temperate regions indicate that the carbamate insecticide aldicarb and its metabolites leach readily through agricultural soils into groundwater. However, little is known about the fate of this nematicide in tropical regions, where its leaching potential may be even greater because of high annual rainfall and the acidic nature and low organic content of many tropical soils. Examination of the leaching behaviour of aldicarb and its metabolites in columns containing soil from Belize, Central America, indicated that total carbamate residues (TCR) could rapidly reach concentrations > 15 mg L^?1 in porewater 1 m below the soil surface within 70 days of application. These values are well in excess of the US EPA Health Advisory level of 0.01 mg L^?1. TCR retention within a given depth interval in the soil columns relative to incoming TCR flux was greatest between 0 and 0.1 m, reflecting high organic matter contents in the upper soil. Retention below 0.1 m was relatively consistent with depth, while differences in relative retention between columns were due to a greater duration of leaching for the second column. Aldicarb was rapidly oxidized to aldicarb sulfoxide and aldicarb sulfone in these soils. The high concentration and mobility of TCR in this acidic soil is attributed to the transformation of the parent compound to the sulfoxide metabolite, which has a lower degradation rate and organic carbon partioning coefficient than aldicarb.     

Simulation of calcium leaching and desorption in an acid forest soil

The aim of the study was to evaluate effects of mobile and immobile water and diffusion‐limited transport on the binding and release of ions in soils. The desorption and leaching of calcium in a humic layer of a densely rooted acid forest soil under a beech stand was studied in laboratory experiments by leaching soil columns with a desorption solution and recycling the leachate through the columns. Radioactive tracers were added and monitored in the leachate to evaluate desorption and leaching characteristics of the soil. Parallel experiments were conducted with chloride and calcium to determine transport and desorption parameters independently. The experimental data were then analysed with a transport model, taking into account effects of mobile and immobile soil water fractions, and in the case of calcium assuming an equilibrium Langmuir adsorption isotherm. The transport was highly dependent on the mobility of the soil water, and in particular the fraction of the soil water to which the chemical was confined as a result of ionic properties. For chloride an excluded soil water phase had to be taken into account to explain the experimental findings. Immobile or mobile water and solute transfer and transport properties were not sufficient to explain non‐equilibrium effects in the adsorption reactions. Desorption curves agreed with results from batch experiments, provided the leaching experiments were done in such a way that equilibration between the soil solution and the solid matrix adsorption sites was reached, otherwise desorption was delayed and the calculated isotherms do not represent actual equilibrium adsorption–desorption conditions.     

石油污染盐碱土壤的淋洗施肥修复

采用淋洗施肥修复方法处理石油污染盐碱土壤,评价该修复方法对石油污染盐碱土壤的修复效果,并且采用最大或然数法和Biolog方法对土壤微生物数量和微生物群落水平生理特性进行研究。结果表明,经过182d的培养,淋洗施肥处理中油和脂的降解率分别比对照处理和施肥处理高（19.7±4.3）%和（13.8±3.4）%,土壤盐分去除率分别比对照处理和施肥处理高（66.5±2.9）%和（41.3±6.2）%,说明该处理是一种修复石油污染盐碱土壤的有效方式。淋洗施肥处理明显提高异养细菌、石油烃降解菌、烷烃降解菌和多环芳烃降解菌数量和土壤微生物活性,促进了微生物对土壤中油和脂的降解。此外,淋洗施肥处理提高了土壤微生物Shannon多样性指数和Simpson指数,促进了微生物种群的稳定,这暗示着土壤微生物种群正在逐渐恢复。