Bound and unextractable pesticidal plant residues: chemical characterization and consumer exposure

Plants are well known to incorporate pesticides into bound and unextractable residues that resist solubilization in common laboratory solvents and are therefore not accessible to standard residue analysis. A characterization of such residues has been proposed for incorporation rates above trigger values of 0.05 mg kg(-1) parent pesticide equivalents, or percentage values of 10% (United States Environmental Protection Agency, 1995) or 25% (Commission of the European Communities, 1997) of the total radioactive residue. These trigger values are often exceeded. The present review describes the current status of the chemical characterization and animal bioavailability of bound and unextractable residues that may be xenobiotic in nature or result from natural recycling of simple degradation products. The latter case represents a mechanism of detoxification. Bound residues have been shown to be covalent or non-covalent in nature. With regard to the plant matrix molecules involved, incorporation into proteins, lignins, pectins, hemicelluloses and cutins has been demonstrated, and four covalent linkage types are known. Animal feeding experiments have revealed cases of low as well as high bioavailability. Many of the studies are limited by experimental uncertainties and by results only being reported as relative percentage values rather than absolute exposure. A preliminary value of absolute exposure from bound and unextractable residues is derived here for the first time from eight case studies. The mean exposure (ca 1.5 mg kg(-1) pesticidal equivalents) exceeds some of the existing maximum residue levels (MRLs) of residual free pesticides that are typically in the range of 0.05-1 mg kg(-1). A mathematical framework for the correction of current maximum residue levels is presented for cases of highly bioavailable bound residues. As bound pesticidal residues in food plants could represent a source of significant consumer exposure, an experimental test scheme is proposed here. It consists of basic chemical characterization, model digestibility tests and, in exceptional cases, animal bioavailability and additional toxicological studies.     

Exposure to sulfosulfuron in agricultural drainage ditches: field monitoring and scenario-based modelling

Field monitoring and scenario-based modelling were used to assess exposure of small ditches in the UK to the herbicide sulfosulfuron following transport via field drains. A site in central England on a high pH, clay soil was treated with sulfosulfuron, and concentrations were monitored in the single drain outfall and in the receiving ditch 1 km downstream. Drainflow in the nine months following application totalled 283 mm. Pesticide lost in the first 12.5 mm of flow was 99% of the total loading to drains (0.5% of applied). Significant dilution was observed in the receiving ditch and quantifiable residues were only detected in one sample (0.06 microg litre(-1)). The MACRO model was evaluated against the field data with minimal calibration. The parameterisation over-estimated the importance of macropore flow at the site. As a consequence, the maximum concentration in drainflow (2.3 microg litre(-1)) and the total loading to drains (0.76 g) were over-estimated by factors of 2.4 and 5, respectively. MACRO was then used to simulate long-term fate of the herbicide for each of 20 environmental scenarios. Resulting estimates for concentrations of sulfosulfuron in a receiving ditch were weighted according to the prevalence of each scenario to produce a probability distribution of daily exposure.     

浅议农药危险性的管理

本文讨论了农药的危险性管理随着管理制度不同而不同．且取决于其暴露途径和机会,建议不要重复管理,尽快与国际接轨,完善我国相关技术标准,提高测试水平。     

《园林史》课程教学的优化途径探讨

我国园林教育发展迅速,很多高校开设了园林相关专业,园林史是园林专业的基础课程。文章针对学生学习兴趣不高的问题,通过分析课程自身特点,阐述学习园林史的必要性,通过丰富文化背景、比较风格差异、注意中西方接驳、增加现代内容来更新和完善教学内容,采用动静相宜、讲赏析结合及角色互换等方式改革和优化教学方法,探索园林史教学的优化途径,取得良好的教学效果,以期为园林史教学提供参考。     

Pharmacokinetic and pharmacodynamic modelling of intravenous,intramuscular and subcutaneous buprenorphine in conscious cats

ObjectiveTo describe simultaneous pharmacokinetics (PK) and thermal antinociception after intravenous (IV), intramuscular (IM) and subcutaneous (SC) buprenorphine in cats.Study designRandomized, prospective, blinded, three period crossover experiment.AnimalsSix healthy adult cats weighing 4.1 ± 0.5 kg.MethodsBuprenorphine (0.02 mg kg^?1) was administered IV, IM or SC. Thermal threshold (TT) testing and blood collection were conducted simultaneously at baseline and at predetermined time points up to 24 hours after administration. Buprenorphine plasma concentrations were determined by liquid chromatography tandem mass spectrometry. TT was analyzed using anova (p < 0.05). A pharmacokinetic-pharmacodynamic (PK-PD) model of the IV data was described using a model combining biophase equilibration and receptor association-dissociation kinetics.ResultsTT increased above baseline from 15 to 480 minutes and at 30 and 60 minutes after IV and IM administration, respectively (p < 0.05). Maximum increase in TT (mean ± SD) was 9.3 ± 4.9 °C at 60 minutes (IV), 4.6 ± 2.8 °C at 45 minutes (IM) and 1.9 ± 1.9 °C at 60 minutes (SC). TT was significantly higher at 15, 60, 120 and 180 minutes, and at 15, 30, 45, 60 and 120 minutes after IV administration compared to IM and SC, respectively. IV and IM buprenorphine concentration-time data decreased curvilinearly. SC PK could not be modeled due to erratic absorption and disposition. IV buprenorphine disposition was similar to published data. The PK-PD model showed an onset delay mainly attributable to slow biophase equilibration (t_1/2k_e0 = 47.4 minutes) and receptor binding (k_on = 0.011 mL ng^?1 minute^?1). Persistence of thermal antinociception was due to slow receptor dissociation (t_1/2k_off = 18.2 minutes).Conclusions and clinical relevanceIV and IM data followed classical disposition and elimination in most cats. Plasma concentrations after IV administration were associated with antinociceptive effect in a PK-PD model including negative hysteresis. At the doses administered, the IV route should be preferred over the IM and SC routes when buprenorphine is administered to cats.     

Reproduction in the Rock Hyrax (Procavia Capensis)

Irradiation has adverse effects on reproductive aspects such as spermatogenic cell population and cell malformation, leading to reduced sperm count and non-viable spermatozoa. This has overshadowed possible effects of radiation exposure on biochemical environment throughout the epididymis and the viability of spermatozoa that appeared morphologically normal. The effects of radiation exposure on sperm quality were evaluated through mating trials and assessment of the cauda epididymal sperm motility. Sprague Dawley rats with body mass of 300–400 g were selected at random. Two experimental groups received acute ⁶°Co γ-radiation doses of 3.5 and 6.0 Gy, respectively. Data were collected 2, 7, 14, 21, 28 and 35 days post-irradiation. Each male was housed with a non-irradiated super-ovulated female during mating trials. Cauda epididymal sperm motility was assessed with the CASMA. Hormone analyses were carried through chemiluminescence diagnostic tests to determine the endocrine status. Results suggest that irradiation causes an overproduction of estrogens, which suppresses the hypothalamic-pituitary axis and inhibits LH and FSH secretions. Both LH and FSH deficiencies have negative effects on the testicular index and local reproductive hormones. Elevated estrogen levels influenced the epididymal internal milieu negatively, resulting in rigid, flagella bending sperm tail, impaired progressive movement of the spermatozoa and hence infertility     

不同条件下2-苯氧乙醇对扁吻鱼幼鱼的麻醉效果

以麻醉剂2-苯氧乙醇浓度(50、100、200、400、600、800、1 000μL/L)、暴露时间(2、4、8、12、16、32 min)和溶解氧浓度(4、8、12、16、18、22 mg/L)作为参考指标,研究2-苯氧乙醇对扁吻鱼(Aspiorhynchus laticeps)幼鱼[(9. 91±0. 31) g]的麻醉效果。结果表明:麻醉时间与麻醉浓度呈负相关,复苏时间与麻醉浓度呈正相关。当浓度≤200μL/L,扁吻鱼幼鱼的呼吸频率在初期会下降,随后上升并维持在11次/10 s,当浓度≥400μL/L时,呼吸频率随着麻醉时间的增加下降,直至休克。当浓度为800和1 000μL/L时,幼鱼可在3 min内麻醉,并且在5 min内苏醒,因此,扁吻鱼幼鱼的最适麻醉浓度范围为800～1 000μL/L。在高浓度麻醉下,随着暴露时间的增加,幼鱼的复苏时间减短,当暴露32 min时,幼鱼仅(100. 51±10. 60) s就可以复苏(P 0. 05)。不同氧浓度下,幼鱼的复苏时间存在差异,其中12 mg/L最低只需(129. 00±36. 50) s,22 mg/L最高需(406. 33±53. 20) s,是12 mg/L的3. 15倍(P 0. 05)。     

底泥中三氯生残留对轮叶黑藻的生态毒性效应

为探讨三氯生(triclosan,TCS)低浓度长期暴露对水生生态系统的毒性效应,本文以典型沉水植物——轮叶黑藻为研究对象,利用HPLC-MS、UV-VIS等分析技术,研究了0.05～0.5 mg·kg~(-1)TCS底泥暴露28 d后轮叶黑藻体内TCS的残留浓度及叶绿素、可溶性蛋白、抗氧化酶活性的变化。结果表明,在处理组中轮叶黑藻叶片中TCS的含量在暴露初期(14 d)呈下降趋势,随着暴露时间延长,叶片中TCS含量逐渐升高,暴露28 d时,0.5 mg·kg~(-1)TCS处理组中轮叶黑藻叶片中TCS浓度高达2.16 mg·kg~(-1)。TCS暴露周期内,轮叶黑藻叶片中叶绿素含量呈持续下降趋势,可溶性蛋白含量呈先促进后抑制的趋势,而其茎部可溶性蛋白含量则始终呈抑制状态。此外,TCS胁迫可显著影响轮叶黑藻叶片和茎部的过氧化氢酶(CAT)、超氧化物歧化酶(SOD)和过氧化物酶(POD)活性,对轮叶黑藻的抗氧化系统造成不可逆的损伤。研究结果为评估水体环境中TCS的生态风险提供了基础数据和理论依据。