14C-甲磺隆在土壤中的可提态残留、结合态残留和矿化

在实验室培养条件下,从质量平衡角度,研究了¹⁴C-甲磺隆在7种土壤中形成结合残留(¹⁴C-BR)、可提态残留(¹⁴C-ER)以及矿化为¹⁴CO₂的规律;同时对¹⁴C-BR的主要影响因子及其在腐殖质中的分布规律进行了研究.结果表明:①¹⁴C-甲磺隆在土壤中形成的¹⁴C-ER,其含量与土壤pH呈显著正相关.甲磺隆母体化合物在7种土壤中 的半减期为13.3～66.6d,降解速率常数λ(d-1)与pH呈显著负相关.②¹⁴C-甲磺隆在7种土壤中形成的¹⁴C-BR,其含量在培养初期的20d内,与土壤pH呈显著负相关且与土壤粘粒含量呈显著正相关;而培养20d后,¹⁴C-BR的含量只与土壤pH呈显著负相关.pH是¹⁴C-甲磺隆在土壤中形成BR的主要影响因子.¹⁴C-甲磺隆在7种土壤中的¹⁴C-BR的最大值约为引入量的19.3%～52.6%.③在整个培养试验过程中,7种土壤中的¹⁴C-BR主要分布在富啡酸和胡敏素中,但其分布在胡敏酸中的相对百分比较小.因此,在¹⁴C-甲磺隆形成BR的过程中,富啡酸的作用＞胡敏素>胡敏酸.④在整个培养试验期间(180d),¹⁴C-甲磺隆在7种土壤中通过三嗪杂环开环矿化为¹⁴CO₂的量约占引入量的12.9%～27.0%,其在碱性土壤中更难被矿化为¹⁴CO₂.     

Identification of the bound residue composition derived from 14C-labeled chlorsulfuron in soil by using LC-MS and isotope tracing method

A new method for extracting the bound residue(BR) derived from ^14C-iabeled chlorsulfuron in soils was developed, and the technique of combining LC-MS with isotope tracing method was subsequently applied to identify the composition of the ^14C-BR in a loamy Fluvent derived from manne deposit. The results showed that the ^14C- [ 2- amino-4- methoxyl-6- methyl- 1,3,5 ]-triazine, ^14C- [ 2-amino-4-hydroxyl-6-methyl-1,3,5]-tdazine and ^14C-chlorsulfuron parent compound constituted the main composition of the ^14C-BR denved from ^14C-labeled chlorsulfuron in the soil. The radioactive ratio of three compounds accounted for 39.8 %, 35.4 % and 17.9 % of total recovered radioactivity, respectively. However, a small amount(3.6 % of total recovered radioactivity) of the complex of ^14C- [ 2-amino-4-hydroxyl-6-methyl-1,3,5]-tdazine might have existed in the ^14C-BR in association with an unknown soil substrate. 2-chlorobenzenesulfonamide was also detected to be one of the components of the BR. The results could well explain the mechanism of phytotoxicity caused by the BR derived from chlorsulfuron in soil. In addition, the mechanism of BR formation in soil was also discussed in details.     

Bioavailability of bound residue derived from 14C-labeled chlorsulfuron in soil and its mechanism of phytotoxicity

The bioavailability of bound residue(BR) derived from ^14C-labeled chlorsulfuron in soil and effect of the main components of the BR on growth of rape( brassica napus) and rice( Oryza sativa L. ) were investigated. The results showed that the BR with the concentration of 0.28 and 0.56 nmol/g air-dried soil, which was calculated by special radioactivity of ^14C-labeled chlorsulfuron parent compound, resulted in significant depression effect on growth of rape seedling. It was assured that the main components(2-amino-4-methoxyl-6-methyl-1,3,5-triazine, 2-amino-4-hydroxyl-6-methyl-1,3,5-triazine, and 2-chloro-benzenesul-fonamide) of the BR did not inhibit the growth of rape and rice. LC-MS analysis demonstrated that the parent compound previously bound to the soil matrix could be again released and transformed into methanol-extractable residue during the course of rape growth. It was concluded that the molecular leading to the phytotoxicity to rape and rice in the BR is still the parent compound.     

氟乐灵在土壤中的结合残留及其对作物的影响

介绍了除草剂氟乐灵在两种土壤中可提部分的消失动态,研究了土壤组分、水分状况及微生物活性对~(14)C-氟乐灵结合残留形成的影响,以及土壤中结合残留物对小麦、黑麦草的有效性.结果表明,有机质含量高的黑土能结合较多的~(14)C-残留物.对含结合残留物的土壤进行高温馏出处理,馏出物的GC检定结果显示除少量母体结构外,氟乐灵主要是通过其代谢物与土壤结合的.盆栽试验表明,氟乐灵结合残留对农作物的生长有明显抑制.     

接种Penicilliumsp.和根际分泌物对土壤甲磺隆的协同降解研究

通过接种Penicillium sp.和模拟小麦根际环境的方法,研究了甲磺隆在Penicillium sp.和小麦根际分泌物协同作用下的生物降解特性.结果表明,根系分泌物丰富了土著微生物和外源微生物,对甲磺隆的降解具有显著的促进作用.接种Penicillium sp.的根际土壤中甲磺隆降解半衰期为8.6 d,其降解速率是接种Penicillium sp.的非根际土壤的1.8倍,是普通根际土壤的2.7倍.继续追加甲磺隆的试验表明,接种菌株Penicillium sp.对甲磺隆的降解具有可持续性.     

应用in vitro法评估土壤性质对土壤中Pb的生物可给性的影响

选取22种典型土壤样品,应用2种in vitro(体外模拟)试验方法——SBET法(simple bioaccessibility extraction test,生物有效性简化提取法)和PBET法(physiologically-based extraction test,生物原理提取法),定量阐明土壤性质对Pb的生物可给性的影响. 结果表明:①SBET法中Pb的生物可给性为18.78%~77.08%,平均值为44.14%;PBET法中Pb的生物可给性为0.72%~50.51%,平均值为13.77%. 除赤红壤和贵州黄壤外,其余20种土壤样品均表现为SBET法中Pb的生物可给性显著高于PBET法,并且随着土壤pH的增长,2种方法的差距更加显著. ②逐步回归分析结果表明,在SBET法中,对土壤Pb的生物可给性影响最大的因子是土壤中w(黏粒),其次为pH,二者可以解释69.49%的Pb的生物可给性的变化;在PBET法中,对土壤Pb的生物可给性影响最大的因子是pH,其次为w(黏粒),二者可以解释73.65%的Pb的生物可给性的变化. 研究结果说明,污染土壤中Pb的生物可给性可以根据土壤pH和w(黏粒)进行预测.      

甲磺隆除草剂的测定方法及其吸附行为研究

采用批量平衡法系统研究了甲磺隆除草剂在几种土壤（熟化红壤、砖红壤性红壤、红筋泥、砖红壤）和矿物（高岭石、针铁矿、和Ca²⁺、Al³⁺、Cu²⁺单离子饱和蒙脱石）上的吸附行为.建立了硼酸-硼砂缓冲液体系的毛细管电泳测定甲磺隆的分析方法.甲磺隆在本实验条件下能够与土壤中的杂质达到基线分离,迁移时间为4.6 min.对比实验表明,毛细管电泳法测定甲磺隆与高效液相色谱法具有一致性.然而,毛细管电泳法能显著节省测试时间和成本,在本类吸附实验研究中具有很好的应用价值.吸附实验数据分析表明甲磺隆的吸附行为都可以用Freundlich模型描述,矿物和土壤的K_f值分别在0.82～199.69和1.97～10.48范围.在几种影响甲磺隆吸附的因素中,pH的影响作用最为显著,说明静电作用可能是甲磺隆在土壤及矿物上吸附的主要机理.     

水稻土中外源Cd老化的动力学特征与老化因子

选择5种不同性质的水稻土,通过外源添加制备了6个不同浓度梯度的Cd污染土壤,研究了外源Cd在几种水稻土中的老化动力学特征与影响因子;同时利用盆栽实验,结合Log-logistic分布模型,研究了5个不同老化时间(14、30、60、90和180d)与土壤中Cd对二种不同Cd敏感性水稻生长毒性的影响.结果表明,不同浓度外源Cd进入土壤后,0.05mol/L EDTA-2Na浸提的有效态Cd含量随着老化时间的增加而逐渐下降;与14d处理相比,老化30d后土壤中有效态Cd降幅达21.5%(红壤)~38.0%(黑土);老化90d后,土壤中Cd进入慢反应阶段. 基于二级动力学方程的拟合参数显示,土壤中Cd的老化特征表现为有效态Cd含量在30~60d内快速降低,随后变化减缓,经过90d的老化后,土壤中有效态Cd含量逐渐趋于平衡.基于老化动力学方程参数(C∞及K2)与土壤性质间的相关性分析表明,土壤pH值是影响Cd有效态含量变化的主控因子,其次是土壤CEC和OC含量.在不同性质土壤中,随着老化时间的增加,土壤中外源Cd对水稻生长毒性的半抑制浓度(EC50)值显著升高;与14d老化处理相比,经过180d老化后土壤中Cd对水稻生长毒性的EC50增加72.1%~195.0%;在大于90d的长期老化过程中,土壤pH值对Cd老化过程的影响逐渐降低,而CEC的影响逐渐上升,尽管如此,土壤中Cd老化过程的主要影响因子仍然是土壤pH,而与测试的2种水稻品种无关.     

河口底泥来源真菌Trichoderma asperellum对壬基酚的降解路径

从壬基酚(Nonylphenol,NP)污染严重的李村河口底泥中分离纯化出可实验室培养的真菌,以高浓度NP为环境选择压力筛选出了一株目标菌株,18S rDNA确定其归属为棘孢木霉(Trichoderma asperellum)。实验室内研究了该菌株对NP的生物降解过程,LC/MS分析其代谢产物,据此提出了NP可能的生物降解路径。菌株的生长曲线表明NP能促进其生长,该菌株3 d对5 mg/L NP的降解率为71.4%,7 d的降解率达到87.2%,14 d则达到了92.2%。LC/MS分析确定了NP四种代谢产物,分别是2-甲基-1-苯基丁醇、3,5-二羟基苯甲酸、苯二酚和苯甲醚(或苄醇)。提出了两种NP可能的生物降解路径,Ⅰ是最终转化成苯二酚,Ⅱ是最终转化成苯甲醚或苄醇。     

Combined effects of two sulfonylurea herbicides on soil microbial biomass and N-mineralization

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骨炭、磷矿粉和生物调理剂对赣南稀土矿区土壤稀土元素淋溶的影响

通过土柱淋溶实验研究了骨炭、磷矿粉与生物调理剂对赣南稀土矿区土壤稀土元素淋溶的影响.结果表明:土壤中添加骨炭、磷矿粉和生物调理剂均显著地提高了淋溶液的p H值.不管是高钇型重稀土土壤还是富镧少钇型轻稀土土壤,添加骨炭均显著地降低了淋溶液中稀土元素的浓度,7 d时淋溶液中15个稀土元素浓度比对照处理降低10.4%~86.7%(重稀土土壤)和4.6%~87.8%(轻稀土土壤),铈、镧、钇、钕、镝、钆等稀土元素浓度降低最明显.培养时间越长稀土元素淋溶量越少,骨炭的降低作用越小.在轻稀土土壤中添加磷矿粉7 d和14 d后,淋溶液中稀土元素浓度均比对照处理有所降低,而在重稀土土壤中添加磷矿粉7~28 d后,均导致淋溶液中稀土元素浓度比对照升高(除了个别元素外).土壤中添加生物调理剂均导致淋溶液中稀土元素浓度急剧提高,7 d时淋溶液中15个稀土元素浓度比对照处理提高0.86~123.4倍(重稀土土壤)和5.4~250.2倍(轻稀土土壤),在重稀土土壤中钇、铒、镱、镝、钆、钕等浓度提高最明显,而在轻稀土土壤中浓度提高最明显的为铈、镧、钕、镨、钆等.另外,还研究了骨炭、磷矿粉和生物调理剂对土壤总稀土元素淋溶的影响.研究表明,骨炭是可以用来修复稀土元素污染土壤的潜力改良剂,而磷矿粉和生物调理剂的应用将提高环境污染的风险.     

淹水条件下不同氮磷钾肥对土壤pH和镉有效性的影响研究

针对稻田土壤镉污染的问题,探讨常用氮、磷、钾肥料品种对土壤镉有效性的影响,采用淹水培养方法,研究了在水稻生长季节施用不同肥料或添加酸、碱对土壤中镉有效性的影响.结果表明,土壤淹水后pH显著增加,特别是培养初期;随着培养时间的延长,pH逐渐回落,并趋向中性.土壤中有效Cd的变化趋势与pH变化趋势相反,两者间存在显著的线性负相关,淹水使土壤有效Cd下降58.2%~84.1%.肥料类型/品种对土壤镉有效性的影响存在显著差异,氮肥的影响较为复杂,钾肥其次,磷肥最小.在所有肥料中,氯化铵对土壤pH降低最多,对Cd的有效性增加最大;其他肥料依次为尿素、过磷酸钙和氯化钾.硫酸铵、硫酸钾和磷酸一铵都显著降低了土壤Cd的有效性.无论是否经过淹水培养,添加酸、碱后土壤pH与土壤有效Cd呈显著负相关,相关系数(R)分别为-0.994和-0.919.本研究进一步表明,在受Cd污染的酸性水稻土上,应避免施用氯化铵,选用含硫肥料,配合施用碱性物质,并在水稻生长过程中保持淹水状态,可有效降低土壤Cd的有效性.     

Effect of two biogas residues’ application on copper and zinc fractionation and release in different soils

Biogas residue (BR) is widely used as a new green fertilizer in agriculture in China. However, it often contains a high concentration of heavy metals so its application should cause our concern. An incubation experiment was conducted to study the risk of pig biogas residue (PBR) and chicken biogas residue (CBR) application on Liuminying soil (LS) and Yixing soil (YS). The soils were incubated for one, three and six months with 0, 2%, 4% and 6% addition of BRs. According to BCR extraction results, the PBR and CBR applications induced an increase in the concentration of exchangeable fraction of Zn. As for the concentration of exchangeable fraction of Cu, an increase was only observed in the treatments with PBR application. The heavy metal binding intensity also showed a similar trend. With the PBR application, for the LS and YS, the highest concentrations of exchangeable Zn increased 3.6 and 9.5 times, respectively, while the exchangeable Cu was increased by 52.6% and 187.1%. Dissolved organic carbon was the limiting factor for the exchangeable Cu while the exchangeable Zn was controlled by soil pH. PBR presented more agricultural risk than CBR when used as fertilizer. Meanwhile, BRs were more adaptable to LS than YS according to the heavy metal release results.     

Alteration of microbial properties and community structure in soils exposed to napropamide

The effect of pesticide napropamide (N,N-diethyl-2-(1-naphthalenyloxy) propanamide) on soil microorganisms for long-term (56 d) was assessed by monitoring changes in soil microbial biological responses. Soils were treated with napropamide at 0, 2, 10, 20, 40, and 80 mg/kg soil and sampled at intervals of 1, 3, 7, 14, 28, 42, and 56 d. The average microbial biomass C declined in napropamide-treated soils as compared to control. The same trend was observed on microbial biomass N after napropamide application.We also determined the basal soil respiration (BSR) and observed a high level in soils treated with napropamide during the first 7 d of experiment. But with the passage of incubation time, BSR with napropamide decreased relatively to control. Application of napropamide at 2–80 mg/kg soil had inhibitory e ects on the activity of urease and invertase. Activity of catalase was enhanced during the initial 7 d of napropamide application, but soon recovered to the basal level. The depressed enzyme activities might be due to the toxicity of napropamide to the soil microbial populations. To further understand the e ect of napropamide on microbial communities, a PCRDGGE- based experiment and cluster analysis of 16S rDNA community profiles were performed. Our analysis revealed an apparent di erence in bacterial-community composition between the napropamide treatments and control. Addition of napropamide apparently increased the number of bands during the 7–14 d of incubation. These results imply that napropamide-induced toxicity was responsible for the disturbance of the microbial populations in soil.     

一株降解邻苯二甲酸酯真菌的筛选及其降解特性研究

采用富集培养法,从PAEs污染的农田土壤中筛选出1株邻苯二甲酸酯类化合物(PAEs)降解真菌F9,经形态学特征及18S rDNA序列分析,初步鉴定为爪哇正青霉(Eupenicillum javanicun).通过正交试验研究,得出菌株F9的最优降解条件是:C:N为20:1、pH为7.0、最佳PAEs初始浓度为50 mg·L^-1.菌株F9对土壤中复合PAEs(DMP、DEP和DOP)有良好的降解效果.在30 d培养期内,可将灭菌土壤中300 mg·kg^-1的PAEs降解65.2%,且培养第一阶段(0~15 d)的降解率远高于第二阶段(16~30 d).     

土壤质地对自养固碳微生物及其同化碳的影响

自养微生物可同化大气中的CO2并将其转化为土壤有机碳,对提高农田土壤的碳吸收和碳储存有重要意义,然而土壤质地对自养固碳微生物功能种群及其同化碳的影响机制还不清楚.本研究选取亚热带地区同一母质发育而成的两种质地水稻土壤(壤质黏土和砂质黏壤土),通过14C-CO2连续标记技术结合室内模拟培养实验,探讨土壤质地对自养微生物同化碳(14C-SOC)、自养微生物截留碳(14C-MBC)和自养微生物可溶性碳(14C-DOC)的影响.以固碳功能基因(cbb L基因)作为指示基因,结合PCR和克隆测序技术,分析不同质地土壤自养固碳微生物群落结构和多样性的差异.结果表明,壤质黏土14C-SOC、14C-MBC和14C-DOC平均含量分别为133.81、40.16和8.10 mg·kg-1,均显著高于砂质黏壤土14C-SOC(104.95 mg·kg-1)、14C-MBC(33.26 mg·kg-1)和14C-DOC(4.18 mg·kg-1)平均含量(P0.05),说明土壤质地显著影响了土壤自养微生物碳同化量以及自养微生物同化碳在土壤中的转化.稀疏曲线、细菌cbb L基因文库覆盖度以及多样性指数分析结果显示壤质黏土固碳细菌群落多样性高于砂质黏壤土.系统发育分析表明,壤质黏土细菌cbb L基因序列与Rhodoblastus acidophilus、Blastochloris viridis、Thauera humireducens、Mehylibium sp.、Variovorax sp.等具有一定的同源性,而砂质黏壤土cbb L基因序列主要与根瘤菌和放线菌同源.可见,土壤质地对自养固碳微生物群落结构和多样性产生了深刻的影响,壤质黏土中较高的黏粒含量、土壤养分含量和阳离子交换量可能有利于维持更高的自养固碳微生物多样性和活性,从而导致不同质地土壤自养微生物碳同化量及其转化存在显著差异.     

Degradation of 14C-glyphosate and aminomethylphosphonic acid (AMPA) in three agricultural soils

Glyphosate (N-phosphonomethyl glycine) is the most used herbicide worldwide. The degradation of 14C-labeled glyphosate was studied under controlled laboratory conditions in three di erent agricultural soils: a silt clay loam, a clay loam and a sandy loam soil. The kinetic and intensity of glyphosate degradation varied considerably over time within the same soil and among di erent types of soil. Our results demonstrated that the mineralization rate of glyphosate was high at the beginning of incubation and then decreased with time until the end of the experiment. The same kinetic was observed for the water extractable residues. The degradation of glyphosate was rapid in the soil with low adsorption capacity (clay loam soil) with a short half-life of 4 days. However, the persistence of glyphosate in high adsorption capacity soils increased, with half-live of 19 days for silt clay loam soil and 14.5 days for sandy loam soil. HPLC analyses showed that the main metabolite of glyphosate, aminomethylphosphonic acid (AMPA) was detected after three days of incubation in the extracts of all three soils. Our results suggested that the possibility of contamination of groundwater by glyphosate was high on a long-term period in soils with high adsorption capacity and low degrading activities and/or acid similar to sandy loam soil. This risk might be faster but less sustainable in soil with low adsorption capacity and high degrading activity like the clay loam soil. However, the release of non-extractable residues may increase the risk of contamination of groundwater regardless of the type of soil.     

理化性质对土壤吸附-解吸苄嘧磺隆的影响

为探讨土壤理化性质对其吸附-解吸BSM(苄嘧磺隆)的影响,采用批量平衡法研究了采自我国东南沿海和中部14个省区的21个土壤样品对BSM的吸附-解吸行为,以及BSM吸附-解吸行为与土壤pH、w(有机质)、w(TN)、w(黏粒)、CEC(阳离子交换量)等理化性质的关系. 结果表明:BSM在土壤中的等温吸附线可用Freundlich方程进行拟合,不同土壤对BSM的吸附强度差异较大,K_f (Freundlich常数)介于0.52~24.05之间. 土壤pH、w(有机质)是影响BSM吸附的主要因素,二者对K_f的解释率为58.1%;土壤对BSM的吸附还受w(TN)、w(黏粒)等的影响. 土壤对BSM的吸附-解吸存在滞后现象,HI(迟滞系数)与土壤pH呈极显著负相关,与w(黏粒)呈显著正相关,其中土壤pH对HI的解释率为33.0%. 吸附平衡溶液pH与K_d (分配系数)呈极显著负相关,对其进行调节可显著改变土壤对BSM的分配能力.      

铅蓄电池厂污染土壤中重金属铅的清洗及形态变化分析

以我国西南某铅蓄电池厂区内不同污染负荷的铅污染土壤为研究对象,对其中铅含量和形态进行分析,并利用不同清洗剂清洗进行筛选.对不同pH条件下铅的清洗效率和铅形态进行分析,并对不同粒径土壤进行不同时间清洗以确定最佳清洗时间.结果表明,厂区内A和B点土壤污染严重,分别达到15 703.22 mg.kg-1和1 747.78 mg.kg-1,活动态铅比例较大,残渣态仅占17.32%、11.64%、14.6%和10.2%.EDTA、盐酸、柠檬酸、鼠李糖脂和SDS这5种清洗剂中EDTA和盐酸的提取效果最好.酸性条件下的清洗不仅能有效地提取铅总量并能有效地减小铅活动态的环境风险,建议pH 4～7最为合适.粗沙粒和细沙粒的清洗效果较好,清洗粉黏粒建议改进工艺,清洗时间定为240 min效果最好.     

Remediation of copper polluted red soils with clay materials

Attapulgite and montmorillonite were utilized to remediate heavy metal polluted red soils in Guixi City, Jiangxi Province, China. The e ects of clay minerals on availability, chemical distribution, and biotoxicity of Cu and Zn were evaluated. The results provided a reference for the rational application of clay materials to remediate heavy metal contaminated soils. From the sorption experiment, the maximum adsorbed Cu2+ by attapulgite and montmorillonite was 1501 and 3741 mg/kg, respectively. After polluted red soil was amended with attapulgite or montmorillonite and cultured at 30 and 60 days, soil pH increased significantly compared to the control. An 8% increase in the amount of montmorillonite in soil and 30 days incubation decreased acid exchangeable Cu by 24.7% compared to the control red soil. Acid exchangeable Cu decreased with increasing amounts of attapulgite and montmorillonite, with best remediation e ect reached at a dose of 8%. Results also showed that the Cu poisoning e ect on earthworms was reduced with the addition of attapulgite and montmorillonite. Montmorillonite showed the best e ect, with the addition of a 2% dose the mortality of earthworms decreased from 60% to zero compared to the control. Our results indicated that the bioavailability of Cu in soils was reduced more e ectively with the application of montmorillonite than attapulgite.