[A环-U-14C]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。     

[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。     

[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。     

[A环-U-~(14)C]丙酯草醚在土壤中的吸附与解吸特性研究

丙酯草醚(ZJ0273)是我国拥有自主知识产权的新型高效油菜田除草剂。本文以[A环-U-14C]丙酯草醚为示踪剂,在实验室模拟条件下,采用液体闪烁测量技术对其在7种土壤中的吸附和解吸特性进行了研究。结果表明:(1)丙酯草醚在7种土壤中的吸附等温线均能极显著符合Freundlich、Langmuir和线性模型,相对而言,前两种模型的相关系数R2(0.9883~0.9998)明显高于线性模型(R2=0.9173~0.9593);(2)丙酯草醚在7种土壤中的解吸等温线能被Freundlich模型和线性模型很好地描述;(3)丙酯草醚极易被土壤吸附,不同类型的土壤对其吸附的差异较大,吸附常数KF与土壤有机质含量呈显著正相关,与之对应的解吸率极低。丙酯草醚吸附解吸过程存在明显的滞后现象,应科学合理地在有机质丰富的土壤中使用。     

丙酯草醚对百合生长的影响及其在鳞茎中的残留

百合田间种植易受杂草危害,为寻求高效低毒、适用于百合生产的新型除草剂及其使用技术,本试验研究了我国创制的新型高效除草剂丙酯草醚对百合田间杂草的控制情况和对其生长的影响规律,同时利用高效液相色谱法检测了其在百合鳞茎中的残留。结果表明,丙酯草醚作为土壤处理剂,于杂草芽前处理,在60 g ai·hm~(-2)用药剂量下能有效防除百合田间禾本科和部分阔叶杂草,杂草鲜重总防效为87.2%;百合田早期喷施丙酯草醚,不仅对百合整个生育期的植株无药害,而且处理组百合在现蕾期、始花期和盛花期的株高、地上部鲜重、花蕾数、花苞数和花朵数均极显著大于对照组,丙酯草醚处理显著促进了百合的生理和生殖生长。高效液相色谱分析结果表明,百合田早期喷施丙酯草醚,在处理组百合鳞茎中未检出丙酯草醚残留(检测限0.001 mg·kg~(-1)FW)。由此可见,丙酯草醚能用于百合田间杂草防除,对百合生长及其食用是安全的。本研究结果为百合田间杂草防除提供了科学依据和技术支持。     

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。     

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。     

土壤中~(14)C-甲磺隆的结合残留及其在腐殖质中的分布规律

实验室培养条件下 ,研究了14 C 甲磺隆在 7种不同类型土壤中形成结合残留( 14 C BR)的规律、主要影响因子及14 C BR在腐殖质中的动态分布规律等。结果表明 :( 1 ) 14 C 甲磺隆在 7种土壤中形成的14 C BR含量在培养初期的 2 0d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 2 0d后 ,14 C BR含量只与土壤pH呈显著负相关。土壤pH是14 C 甲磺隆在土壤中形成BR的主要影响因子。14 C -甲磺隆在各类土壤中的14 C BR的最大值分别占引入量的 48 5%、46 5%、52 6%、1 9 3 %、49 7%、42 0 %和 46 5% ;( 2 )在整个培养试验过程中 ,14 C 甲磺隆在 7种不同类型土壤中的14 C BR ,主要分布在富啡酸和胡敏素中 ,前者中的相对百分比大于后者 ,而在胡敏酸中的相对百分比较小。土壤中14 C 甲磺隆BR的形成过程中 ,富啡酸的作用 >胡敏素 胡敏酸     

[噻唑基-2-14C]-毒氟磷在水-沉积物系统中的降解与残留转化研究

毒氟磷是我国自主创制的新型植物抗病毒剂,研究毒氟磷的环境行为和归趋对科学评价其环境风险具有重要意义。本试验采用¹⁴C同位素示踪技术,以[噻唑基-2-¹⁴C]-毒氟磷为示踪剂,研究了毒氟磷在A和B两种水-沉积物系统中的好氧降解动态以及残留转化规律。结果表明,毒氟磷母体在两种水-沉积物系统中的水相消散和降解均符合一级动力学模型,其水相消散半减期分别为7.23 d (A)和13.86 d (B),在水-沉积物整个系统中的母体降解半减期则分别为121.60 d (A)和65.39 d (B)。毒氟磷在供试水-沉积物系统中的残留转化规律存在显著差异,培养结束时(培养时间为100 d),可提态残留在A和B系统中分别占放射性引入量的77.41%和43.71%,矿化量分别占放射性引入量的1.11%和2.83%,结合态残留分别占放射性引入量的24.11%和49.25%;较高的降解率和阳离子交换量是毒氟磷及其代谢产物在B系统中更易形成结合残留的主要原因。本研究结果为科学评价毒氟磷在水-沉积物系统中的安全性提供了基础数据和科学依据。     

[苄基-14C]-毒氟磷在大豆中的残留分布和代谢产物动态变化

为深入了解毒氟磷在植物体内的残留代谢规律,以大豆为研究对象,利用¹⁴C示踪法研究了[苄基-¹⁴C]-毒氟磷在大豆中的残留分布特征及代谢产物动态变化规律。结果表明,施药后毒氟磷主要残留在大豆受施叶上,在豆叶中毒氟磷母体的半衰期为15.32 d,施药后代谢产物的残留浓度均随时间推移而不断增加;至施药20 d时,叶片上毒氟磷母体的残留浓度为6.960 mg·kg^-1, 占总放射性活度的53.443%;代谢产物M4、M3、M1+M2的残留浓度分别为3.838、2.431、1.464 mg·kg^-1; 收获时,可食豆子中残留物含量小于总放射性残留的0.3%,其代谢产物组成与叶中相同;母体及M4的相对含量分别为51.932%和20.301%,且两者残留浓度均大于0.050 mg·kg^-1。本试验为客观评价毒氟磷的安全性提供了重要的代谢数据。     

Degradation of [14C]phosphinothricin (glufosinate) in soil under laboratory conditions: Effects of concentration and soil amendments on 14CO2 production

Summary Degradation of the herbicide phosphinothricin (L-homoalanine-4-yl-(methyl)-phosphinic acid) in a phaeozem was investigated by monitoring the ¹⁴CO₂ release from [1-¹⁴C] and [3,4-¹⁴C]phosphinothricin. The degradation was largely due to microbial activity, since the rate decreased by more than 95% when the soil was sterilized by -radiation. Data obtained with both labels suggested that decarboxylation of phosphinothricin preceded oxidation of its C-atoms 3 and 4, since a metabolite, probably 3-methylphosphinico-propanoic acid, was only labelled when [3,4-¹⁴C]phosphinothricin was used as the substrate. Maximum rates of ¹⁴CO₂ production from both the 1- and 3,4-label positions occurred without a lag phase during the breakdown of phosphinothricin as monitored for a total of 30 days at 5-day intervals. This result indicated that a phosphinothricin-degrading microbial community was already present in the soil. With low concentrations of [1-¹⁴C]phosphinothricin (10.7 mg kg^-1 soil), complete decarboxylation at 25°C was observed within 30 days of incubation, compared to 15.9% ¹⁴CO₂ release from [3,4-¹⁴C]phosphinothricin. Increasing the quantity of the herbicide in the soil (10.7–1372 mg kg^-1) resulted in increased degradation rates, irrespective of whether the herbicide was labelled in the positions 1 or 3 and 4. Addition of glucose and other carbohydrates stimulated ¹⁴CO₂ release while addition of a yeast extract had a negative effect. Glucose stimulation was reversed by ammonium nitrate, suggesting that the microorganisms were using the herbicide as a source of N.     

Degradation of [carboxyl-14C] 2,4-D and [ring-U-14C] 2,4-D in 114 agricultural soils as affected by soil organic carbon content

This study compared the degradation of [carboxyl-¹⁴C] 2,4-dichlorophenoxyacetic acid (2,4-D) (C2,4-D) and [ring-U-¹⁴C] 2,4-D (R2,4-D) in 114 agricultural soils (0–15 cm) as affected by 2,4-D sorption and soil properties (organic carbon content, pH, clay content, carbonate content, cation exchange capacity, total microbial activity). The sample area was confined to Alberta, Canada, located 49–60° north longitude and 110–120° west latitude and soils were grouped by soil organic carbon content (SOC) (0–0.99%, 1–1.99%, 2–2.99%, 3–3.99% and >4% SOC). Degradation rates of C2,4-D and R2,4-D followed first-order kinetics in all soils. Although total microbial activity increased with increasing SOC, degradation rates and total degradation of C2,4-D and R2,4-D decreased with increasing SOC because of increased sorption of 2,4-D by soil and reduced bioavailability of 2,4-D and its metabolites. Rates of R2,4-D degradation were more limited by sorption than rates of C2,4-D degradation, possibly because of greater sorption and formation of bound residues of 2,4-D metabolites relative to the 2,4-D parent molecule. Based on the sorption and degradation parameters quantified, there were two distinct groups of soils, those with less than 1% SOC and those with greater than 1% SOC. Specifically, soils with less than 1% SOC had, on average, 2.4 times smaller soil organic carbon sorption coefficients and 1.4 times smaller 2,4-D half-lives than soils with more than 1% SOC. In regional scale model simulations of pesticide leaching to groundwater, covering many soils, input parameters for each pesticide include a single soil organic carbon sorption coefficient and single half-life value. Our results imply, however, that the approach to these regional scale assessments could be improved by adjusting the values of these two input parameters according to SOC. Specifically, this study indicates that for 2,4-D and Alberta soils containing less than 1% SOC, the 2,4-D pesticide parameters obtained from generic databases should be divided by 2.5 (soil organic carbon sorption coefficient) and 1.5 (half-life value).     

Formation and degradation of soil-bound [14C] fenitrothion residues in two agricultural soils

The formation of non-extractable residues of [¹⁴C]fenitrothion and their degradation in a black earth and a red yellow podzolic soil was studied. After a 65-day incubation, non-extractable radioactivity represented 73.7 and 59.35% of the applied radioactivity in the black earth and podzolic soil respectively, while evolved ¹⁴CO₂ accounted for only 9.4 and 12.7%. The effects of various amendments and treatments on the degradation of the non-extractable residues to ¹⁴CO₂ was studied. All of the amendments produced a priming effect and significantly increased the formation of ¹⁴CO₂ in both soils. The addition of unlabelled fenitrothion and 3-methyl-4-nitrophenol to the black earth and 3-methyl-4-nitrophenol to the podzolic soil produced the greatest increases in ¹⁴CO₂ evolution. The evidence presented suggests that a part of the unextractable residue is either fenitrothion or 3-methyl-4-nitrophenol.     

[噻唑基-2-14C]-毒氟磷在产蛋鸡体内的分布

为阐明毒氟磷在动物体内的分布代谢特征,并深入认识毒氟磷的安全性和膳食风险,本研究选择白羽产蛋鸡为试验对象,[噻唑基-2-¹⁴C]-毒氟磷为同位素示踪剂,研究了毒氟磷在产蛋鸡体内的排泄分布特征。结果表明,毒氟磷在产蛋鸡体内排泄水平高,首次给药24 h后即排泄出当日给药量的82.04%,连续给药7 d后的累计排泄率为82.24%。毒氟磷在组织中的总残留仅占引入量的3.81%,其中胃中残留量占比相对最高,占引入量的2.14%,而肺、肾、脂肪、胰腺中的放射性残留量均不超过引入量的0.01%,膳食评估结果表明在上述内脏组织中的毒氟磷残留无膳食风险。蛋、肌肉、心、脑、脾、卵巢等组织中未检测到放射性残留。本研究为科学评价毒氟磷在家禽中的安全性提供了试验依据。     

Detection of microbial groups metabolizing a substrate in soil based on the [l4C] quinone profile

Analysis of [^l4C]respiratory Quinones synthesized in soil for 6 h after spiking with [U-¹⁴C]glucose, [U-^l4C]glycine, and [1,2-^l4C]acetate enabled to fingerprint the microorganisms metabolizing each substrate in soil and to determine the whole structure of the microbial communities at the same time. The [^l4C]- Quinones synthesized from [U-^l4C] glucose were the same as those from [U-^l4C] gIycinc in soil, suggesting that the same microbial groups metabolized glucose and glycine under the given conditions. No [^l4C]quinones from [1,2- ¹⁴C] acetate were detected in soil, indicating that the metabolism of acetate by microorganisms is negligible. The profiles of [^l4C]quinones from [U-^l4C]- glucose were compared between Nagoya University Farm soils subjected to 4 different fertilizing practices. The soils receiving farmyard manure contained [^l4C]menaquinones with highly hydrated isoprenoid units, which indicated the presence of Actinobacteria metabolizing glucose. The soil receiving only chemical fertilizers contained [¹⁴C]ubiquinone with 8 isoprenoid units (Q-8), indicating the presence of beta and gamma subdivisions of Proteobacteria. All the 4 soils were characterized by the high proportions of [¹⁴C] MK-6 and a mixture of [^l4C]MK-8(H₄) and [^l4C]MK-9. The Q-9 and Q-10(H₂) indicators of fungi, were not labeled under most of the conditions.