[A环-U-~(14)C]丙酯草醚在土壤中的迁移和淋溶

在实验室模拟条件下,采用同位素成像及液体闪烁测量技术对[A环-U-14C]丙酯草醚在7种土壤中的迁移和淋溶特性进行了研究。结果显示:[A环-U1-4C]丙酯草醚在7种土壤(S1~S7)薄板层析中的Rf值分别为0.36、0.27、0.21、0.31、0.30、0.15和0.24,这表明丙酯草醚在S1中属于中等移动农药,而在其余6种土壤中均属于不易移动农药。结果还表明,[A环-U1-4C]丙酯草醚在7种土壤中随水(最大降雨量200mm/24h)的淋溶性较弱,在S1和S4中其主要分布在0~6cm土层,其余5种土壤中则主要分布在0~4cm土层。丙酯草醚在7种供试土壤中的最大淋溶量峰值均出现在0~2cm表层。因此,从迁移和淋溶特性看,田间使用丙酯草醚不易对地下水造成污染。     

菲在土壤/沉积物上的吸附-解吸过程及滞后现象的研究

实验研究了菲在土壤 /沉积物上的吸附 解吸过程。CHL土壤和HFH沉积物中有机质的固相13 CCPMASNMR谱图很相似 ,表明样品中有机质的组成差异不大 ;菲在土壤 /沉积物上的吸附过程表现出明显的非线性 ;线性模型不适合拟合菲的吸附等温线 ,Freundlich模型和双区位反应模型 (DRDM)较好地拟合了菲的吸附等温线 ,其中DRDM模型还清楚地反映菲在低浓度和高浓度下不同的吸附方式 ;另外 ,研究表明菲在土壤 /沉积物上的解吸过程中存在明显的滞后现象 ,这可能和土壤 /沉积物有机质的异质性和土壤胶团微小孔隙的存在有关。     

~(14)C-红霉素在土壤中的吸附解吸和淋溶特性

为探究抗生素在土壤中的吸附、解吸及其淋溶迁移行为,采用振荡平衡法和土柱淋溶法分别研究了~(14)C-红霉素在7种不同类型土壤中的吸附、解吸和淋溶特性。吸附试验结果表明,红霉素在7种土壤中的等温吸附-解吸规律满足Freundlich、Langmiur和线性模型,相关系数R~2为0.9810~0.9999。土壤性质对红霉素的吸附性能有显著影响,7种土壤中吸附常数Kf值依次为S_6S_3S_7S_5S_2S_4S_1。相关性分析表明,Kf值与土壤有机质含量呈正相关(r=0.956,P0.01),而与土壤pH值、阳离子交换量、粘粒含量无显著相关性。红霉素在7种土壤中的吸附自由能变化均小于40 k J·mol~(-1),表明其在土壤中的吸附机制主要为物理吸附。红霉素在7种土壤中的解吸均存在明显的滞后现象。土柱淋溶试验结果表明,红霉素在7种土壤中淋溶性均较弱,66.86%~92.53%的量集中在0~5 cm表层土壤中。总体上红霉素在土壤S_1、S_2和S_4中的淋溶能力最强,其次为S_3、S_5和S_7,在S_6中最不易淋溶,与吸附试验结果相一致。综合红霉素在土壤中的吸附、解吸和淋溶特性,红霉素在土壤中较难淋溶,使其可能在土壤介质中积累,存在一定的环境污染风险。本研究结果对评估环境安全性具有重要意义。     

天然土壤中典型多溴联苯醚解吸过程的初步研究

选择5种有机质含量不同的天然土壤,采用批量实验方法考察典型多溴联苯醚8DE47的解吸行为,并尝试利用非线性Freundlich模型和线性模型模拟不同初试浓度条件下BDE47的土壤解吸过程。针对较为显著的器壁吸附影像,所有检测数据均进行器壁吸附定量修正。结果表明,BDE47土壤解吸过程总体分为初始的快解吸和后续的慢解吸两个阶段。在初始阶段,BDE47解吸过程表现为线性行为,但非线性特征随解吸时间延长呈现增强趋势。土壤有机质（用TOC表征）释放的溶解有机质是影响土壤中BDE47解吸行为差异的主要因素之一。     

阿特拉津对绿麦隆吸附-解吸作用的影响

采用批平衡实验,研究绿麦隆在单一及复合污染体系中的吸附-解吸行为。结果表明,无论是单一体系还是复合体系,吸附等温线均可用Freundlich模型进行良好的拟合。随着阿特拉津浓度的增加,土壤对绿麦隆的吸附作用降低,表明绿麦隆和阿特拉津之间存在竞争吸附,这可能与土壤的有机质类型和绿麦隆、阿特拉津的性质、结构有关。解吸实验表明,随着阿特拉津的浓度增加,绿麦隆的解吸作用增加。吸附过程的拟合指数n值大于解吸过程的对应值,即绿麦隆在不同体系中的解吸作用均存在一定的滞后性。应用Freundlich解吸等温线参数对吸附-解吸等温线的滞后作用进行量化,CT、（CT＋0.5AT）、（CT＋1AT）和（CT＋2AT）处理解吸等温线的滞后系数ω分别为165.200,146.132,94.534和85.945,即随阿特拉津浓度增加,绿麦隆解吸等温线的滞后性降低。     

小麦微粒体对丙酯草醚的代谢作用初探

用5%乙醇和10mmol/L丙酯草醚诱导的小麦黄化苗茎部制备微粒体,与[C环-U1-4C]丙酯草醚保温反应,产物经乙酸乙酯萃取,HPLC-LSC分离测定,最后用HPLC-MS鉴定其分子结构,发现了3种与Smiles重排相关的14C标记丙酯草醚代谢物(Y1,Y2和Y3),据此推测丙酯草醚在小麦微粒体(细胞色素P450酶系)的作用下进行了羟基化。研究结果还表明,微粒体反应体系可能也有助于丙酯草醚的异构化作用。     

五氯酚在酸性土壤表面的吸附-解吸特征研究

本实验研究五氯酚在江西红壤和南京黄棕壤表面的吸附-解吸特征,结果表明:Freundlich和Langmuir等温吸附方程均能较好地描述PCP在两种土壤表面的吸附,且黄棕壤表面的最大吸附量大于红壤。用动力学方程对PCP在红壤中的吸附过程进行拟合,Elovich方程、双常数方程和一级动力学方程均得到较好的结果,其相关系数(R2)在0.96 ~ 0.99之间,达到极显著水平。Elovich方程反映出PCP在土壤表面吸附的能量非均质分布;而抛物线扩散方程不能描述PCP的吸附过程,其相关系数0.46 ~ 0.48。PCP在土壤中的解吸率与有机质含量和pH值相关,随有机质含量增加,PCP解吸率降低,即黄棕壤表土<黄棕壤底土,红壤表土<红壤底土;随模拟酸雨的pH值降低,土壤因对PCP的吸附能力增加,其解吸率降低。     

土壤中黑碳对农药敌草隆的吸附-解吸迟滞行为研究

采用批处理振荡法和连续稀释法分别测定了敌草隆在人工添加黑碳土壤和自然形成的不同有机质和黑碳含量的土壤中的吸附一解吸行为。吸附结果表明，人工添加黑碳的土壤对敌草隆的吸附强度和吸附容量以及吸附等温线的非线性均随土壤黑碳添加浓度的增加而逐步增大；自然土壤的吸附容量和吸附强度随土壤总有机质含量增加而增加，但吸附等温线的非线性则与土壤中黑碳对有机质的相对含量有关，黑碳比例越高，等温线非线性越大。解吸实验结果表明，无论是人工添加黑碳的土壤还是自然土壤，对敌草隆的解吸迟滞作用均随土壤黑碳含量增高而愈明显。     

新型除草剂丙酯草醚的微量合成

从苯酚、对氨基苯甲酸和2-甲硫基-4,6-二氯嘧啶出发,建立了包含取代、氧化和缩合等7步反应的丙酯草醚除草剂微量制备方法。最终产物经制备HPLC纯化,其收率为53%,化学纯度大于98%,用MS(EI)、HPLC-MS1、H-NMR、UV等方法确认了丙酯草醚的结构。所建立的丙酯草醚微量制备方法,为放射性同位素标记丙酯草醚的合成奠定了基础。     

酰胺类除草剂在土壤上吸附的位置能量分布分析

根据异丙甲草胺、乙草胺、丙草胺和丁草胺在六种土壤上的等温吸附结果 ,计算了它们在六种土壤上的位置能量分布和有机质标化的平均分配常数。结果表明 :四种除草剂在六种土壤上的吸附等温线为Freundlich型 ;低浓度范围内 ,农药在土壤上的吸附首先发生在土壤表面的高能吸附位置上 ;土壤表面位置能量分布的具体情况与被吸附农药性质有关 ;土壤上的吸附位置数或吸附容量主要与土壤有机质含量有关 ,粘土对吸附也有一定的贡献 ;疏水键合机理在四种酰胺类除草剂吸附过程中起着重要的作用     

[C环-U-14C]丙酯草醚在油菜和水稻中的吸收、运转及分布

丙酯草醚(ZJ0273)是我国创制的一种新型高效油菜田除草剂。本文以[C环-U-14C]-ZJ0273为示踪剂,在实验室条件下,对丙酯草醚在敏感性植物水稻和耐性植物油菜中的吸收、运转及分布规律进行了研究。结果表明:(1)施药后,水稻和油菜对丙酯草醚的吸收量总体呈随时间增加而增加的趋势,且前者大于后者。至384h,水稻对丙酯草醚的吸收量为24.1%,而油菜仅为4.1%,水稻约为油菜的5.88倍。(2)丙酯草醚被油菜和水稻根系吸收后,均主要分布在根部,不易向上运转。水稻根系与地上部(茎叶)的放射性分布比为7.10∶1,油菜则为4.44∶1;水稻和油菜根系中单位质量放射性活度分别是各自地上部的10.36和9.85倍。(3)水稻根系和茎叶单位质量放射性活度分别为9.470 Bq/mg和0.910 Bq/mg,显著高于油菜的3.870 Bq/mg和0.390 Bq/mg。水稻与油菜对丙酯草醚吸收量以及单位质量中积累量的差异可能是丙酯草醚对两者存在选择性的原因之一。     

好氧土壤中[C环-U-14C] 丙酯草醚的结合残留及其在腐殖质中的分布动态

农药的环境行为与归趋,尤其是结合残留研究,是新农药安全性评价的重要内容之一,这关系到新农药的科学使用。本文利用14C同位素示踪技术,研究了[C环-U-14C]丙酯草醚(ZJ0273)在3种不同类型好氧土壤中的结合残留及其在富啡酸、胡敏酸和胡敏素中的动态分布。结果表明：（1）在整个培养过程中,土壤中的丙酯草醚结合残留量均随时间而递增。培养至75d,红砂土（S1）、黄松土（S2）与淡涂泥田（S3）中的14C-BR最大值分别为引入量的12.55%,20.35%和20.49%,且富含有机质和pH较高的土壤更易与丙酯草醚形成结合残留;（2）丙酯草醚与富啡酸、胡敏酸和胡敏素形成的结合残留,含量大小依次为富啡酸＞胡敏素＞胡敏酸。因此,丙酯草醚与土壤基质形成结合残留的过程中,富啡酸起主要作用,而胡敏酸的作用最小。     

[C环-U-14C]丙酯草醚在油菜/水稻中的吸收、运转及分布

丙酯草醚(ZJ0273)是我国创制的一种新型高效油菜田除草剂。本文以[C环-U-14C]丙酯草醚为示踪剂,在实验室条件下,对丙酯草醚在敏感性植物水稻和耐性植物油菜中的吸收、运转及分布规律进行了研究。结果表明：（1）施药后,水稻和油菜对丙酯草醚的吸收量总体呈随时间增加而增加的趋势,且前者大于后者。至384 h,水稻对丙酯草醚的吸收量为24.1%,而油菜仅为4.1%,水稻约为油菜的5.88倍。（2）丙酯草醚被油菜和水稻根系吸收后,均主要分布在根部,不易向上运转。水稻根系与地上部（茎叶）的放射性分布比为7.10︰1,油菜则为4.44︰1;水稻和油菜根系中单位质量放射性活度分别是各自地上部的10.36和9.85倍。（3）水稻根系和茎叶单位质量放射性活度(分别为9.470 Bq/mg和0.910 Bq/mg)显著高于油菜(3.870 Bq/mg和0.390 Bq/mg)。水稻与油菜对丙酯草醚吸收量以及单位质量中积累量的差异可能是丙酯草醚对两者存在选择性的原因之一。     

ALA提高丙酯草醚胁迫下油菜幼苗耐性研究

对油菜幼苗叶面喷施不同浓度的丙酯草醚(ZJ0273)和5-氨基乙酰丙酸(ALA),研究了ALA与丙酯草醚协同处理对苗期的油菜是否安全。结果表明,丙酯草醚随浓度从100~1000mg/L变化,逐渐抑制油菜幼苗生长,鲜重减少,净光合速率和叶绿素含量降低;过氧化物酶(POD)、超氧化物歧化酶(SOD)和抗坏血酸过氧化物酶(APX)活性下降,丙二醛(MDA)积累提高。而10~100mg/L的ALA则促进油菜幼苗生长,增加植株的鲜重、净光合速率并提高了叶绿素含量,POD、SOD和APX酶活性均比对照显著提高,MDA积累减少;500mg/L的ALA效果相反,表现为抑制作物生长。100mg/L ALA和不同浓度的丙酯草醚协同处理,油菜幼苗均比对照生长的更好,鲜重增加,净光合速率提高,抗氧化酶活性增加,MDA积累减少。因此,ALA可以提高油菜幼苗在除草剂丙酯草醚胁迫下的耐性。     

Soil metabolism of a new herbicide, [14C]Pyribenzoxim, under flooded conditions

To elucidate the fate of a new pyrimidinyloxybenzoic herbicide, pyribenzoxim, a soil metabolism study was carried out with [14C]pyribenzoxim applied to a sandy loam soil under flooded conditions. The material balance of applied radioactivity ranged from 96.4 to 104.4% and from 96.1 to 101.9% for nonsterile and sterile soils, respectively. The half-life of [14C]pyribenzoxim was calculated to be approximately 1.3 and 9.4 days for nonsterile and sterile soils, respectively. The metabolites identified during the study were 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (M1) and 2-hydroxy-6-(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (M2), resulting from the cleavage of the ester bond and subsequent hydrolysis. The nonextractable radioactivity levels increased to 37.8% for nonsterile conditions at 50 days after treatment and to 38.2% for sterile conditions at 60 days after treatment. Fractionation of the nonextractable soil residues indicated that bound radioactivity was associated mainly with humin fraction. No significant volatile products or [14C]carbon dioxide was observed during the study. On the basis of these results, pyribenzoxim is considered to undergo rapid degradation in soil by microbial and chemical reactions, mainly hydrolysis, which limits its transfer to and accumulation in lower soil layers and groundwater. Therefore, the possibility of environmental contamination from the use of pyribenzoxim is expected to be very low.     

Metabolism of a new herbicide, [(14)c]pyribenzoxim, in rice

The in vivo metabolism of a new herbicide pyribenzoxim (benzophenone Ο-[2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoyl]oxime) in rice was carried out using container trials. Two radiolabeled forms of [carbonyl-(14)C]pyribenzoxim (P1) and [ring-(14)C(U)]pyribenzoxim (P2) were treated separately as formulations for foliar treatment by single applications of 50 g of active ingredient (ai)/ha at the 4-6 leaves stage. At 0, 7, 30, and 60 days after treatment (DAT), samples of panicle, foliage/rest of plant, and roots were taken for analysis. Upon harvest (120 DAT), rice plants were separated into grain, husk, straw, and root parts. Total radioactive residues (TRRs) at each sampling date were determined to show that the final radioactive residues at harvest were low in grain, husk, straw, and roots, accounting for <17 ppb. The concentration of final residues in the rice plant decreased rapidly, and less than 0.1% of initial TRRs remained at harvest. At 7 DAT, metabolite 1 [M1, 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid] and two unknown compounds (other-1 and other-2) were detected in foliage extract, accounting for 3.5% TRRs (21.0 ppb), 3.1% TRRs (19.0 ppb), and 9.0% TRRs (54.3 ppb), respectively, while 26.1% of M1 was observed in solvent wash. Any other metabolites were not detected in the plant, including expected metabolite M3 (benzophenone oxime). On the basis of the results obtained, a metabolic pathway of pyribenzoxim in a rice plant was proposed.     

Identification of rat urinary and fecal metabolites of a new herbicide, pyribenzoxim

Rats were treated with pyribenzoxim (O-[2,6-bis[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoyl]oxime), a new herbicide, to investigate the related metabolites in urine and feces. Metabolites were identified using LC/MS (electrospray ionization) and GC/MS (electron impact ionization) following the relatively simple and rapid extraction and purification procedures. Three metabolites were identified in urine either from oral gavage or intravenous (iv) injection. They were benzophenone oxime (BO), benzophenone oxime glucuronide (BOG), and 2-hydroxy-6-(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (HDB). Benzophenone oxime was present in larger quantity than BOG and HDB in urine from oral treatment, while the case was opposite in urine from iv treatment. Glucuronide conjugate was confirmed unambiguously by enzyme hydrolysis. 2,6-Bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (KIH-2023) and benzophenone were identified in feces. Benzophenone was confirmed by GC/MS and HPLC/DAD since LC/MS could not produce an ESI spectrum. On the basis of the results obtained, a metabolic map of pyribenzoxim is proposed.     

Aerobic biodegradation kinetics and pathway of the novel herbicide ZJ0273 in soils

Degradation of ZJ0273, a recently developed pyrimidynyloxybenzoic‐based herbicide, was investigated in five different soils under aerobic conditions. ZJ0273 degradation rate was strongly affected by soil physico‐chemical characteristics and the inoculation of ZJ0273‐degrading bacteria. Greater organic matter (OM) content, neutral pH and inoculation of ZJ0273‐degrading bacteria can increase degradation rate and decrease the half‐life value (DT50). At 30°C the biodegradation rate of ZJ0273 reached 41–85% in natural (unsterilized) soils. It ranged from 69 to 96% at 90 days after treatment (DAT) in five different types of soils after re‐inoculation of Amycolatopsis sp. M3‐1 and DT50 decreased by 34 , 81, 16, 20 and 32 days, respectively, in soils S1, S2, S3, S4 and S5. Furthermore, using the six metabolites (M1–M6) identified six metabolites (M1–M6) by liquid chromatography‐mass spectrometry (LC‐MS) and their behaviour, a biodegradation pathway of ZJ0273 in soils was proposed. New metabolites, M5 and M6, were found in soils. Biodegradation of ZJ0273 involved continuous biocatalytic reactions, such as de‐estering, hydrolysis, acylation, C‐N cleavage, de‐methyl and ether cleavage reactions. Finally, ZJ0273 was bio‐transformed into M4 and M6, which could be degraded and oxidized into CO₂ and H₂O through the tricarboxylic acid (TCA) cycle.     

Aerobic soil metabolism of a new herbicide,LGC-42153

To elucidate the fate of a new sulfonylurea herbicide, LGC-42153 [N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-2-(1-methoxyacetoxy-2-fluoropropyl)-3-pyridinesulfonamide], in soil, an aerobic soil metabolism study was carried out for 120 days with [(14)C]LGC-42153 applied to a loamy soil. The material balance ranged from 90.7 to 101.5% of applied herbicide. The half-life of [(14)C]LGC-42153 was calculated to be approximately 9.0 days. The degradation products resulted from the cleavage of the sulfonylurea bridge. The metabolites identified during the study were N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-2-(1-hydroxy-2-fluoropropyl)-3-pyridinesulfonamide, 2-(1-hydroxy-2-fluoropropyl)-3-pyridinesulfonamide, and 4,6-dimethoxy-2-aminopyrimidine. No significant volatile products or [(14)C]carbon dioxide was observed during the study. Nonextractable (14)C-residue reached 14.4-30.5% of applied material at 120 days after treatment, and radioactivity was distributed mostly in the humin and fulvic acid fractions.