土壤和堆肥中四环素类抗生素的检测方法优化及其在土壤中的降解研究

在对土霉素(OTC)、四环素(TC)和金霉素(CTC)3种四环素类抗生素的高效液相色谱(HPLC)检测分析方法以及在土壤和堆肥中的提取方法进行改进和优化的基础上,采用该方法进行了3种抗生素在土壤中的降解试验。结果表明,选用Agilent Eclipse XDB-C8(4.6×150 mm,5μm)色谱柱,以0.01 mol/L草酸/乙腈/甲醇(79/10.5/10.5,v/v/v)为流动相,紫外检测波长268 nm,流速1.0 mL/min,进样量5μL,采用外标法定量,可使3种四环素类抗生素在20 min内全部洗脱并达到基线分离;在0～10 mg/L范围内,抗生素浓度与峰面积呈显著的线性关系,相关系数(r)均0.999。土壤和堆肥样品中的OTC、TC和CTC可用1 mol/L NaCl/0.5 mol/L草酸/乙醇(25/25/50,v/v/v)混合溶液提取,其回收率在76.0%～92.5%之间。加入到土壤中的抗生素在25℃下避光培养49 d后,在壤土和红土中的降解率分别是67%～72%和36%～46%,对应的半衰期分别为26～30 d和46～75 d,说明抗生素在壤土中比红土中容易降解。此外,3种抗生素在壤土中的半衰期没有显著性差异,而在红土中CTC和TC的降解速率显著高于OTC。     

重庆市马铃薯测土配方施肥指标体系构建

采用土壤养分丰缺指标法,对重庆市马铃薯"3414"试验数据进行统计分析,以相对产量55%、65%、75%、85%和95%划分土壤养分分级指标,并分别以三元二次、一元二次和线性加平台模型对各试验点施肥量与产量关系进行模拟,选择最优模型计算最佳施肥量,建立了重庆市马铃薯测土配方施肥指标体系。结果表明,当土壤碱解氮含量处于极低等级(<90mg/kg)、低等级(90～110mg/kg)、较低等级(110～140mg/kg)、中等级(140～170mg/kg)、较高等级(170～210mg/kg)、高等级(>210mg/kg)时,马铃薯氮肥(N)每667m2推荐施用量分别为10～12kg、8～10kg、7～8kg、6～7kg、4～6kg、0～4kg;当土壤有效磷含量处于极低等级(<5mg/kg)、低等级(5～10mg/kg)、较低等级(10～15mg/kg)、中等级(15～20mg/kg)、较高等级(20～25mg/kg)、高等级(>25mg/kg)时,马铃薯磷肥(P2O5)每667m2推荐施用量分别为8kg、7～8kg、6～7kg、5～6kg、4～5kg、0～4kg;当土壤速效钾含量处于极低等级(<30mg/kg)、低等级(30～50mg/kg)、较低等级(50～80mg/kg)、中等级(80～130mg/kg)、较高等级(130～210mg/kg)、高等级(>210mg/kg)时,马铃薯钾肥(K2O)每667m2推荐施用量分别为11～12kg、9～11kg、7～9kg、6～7kg、4～6kg、0～4kg。     

畜禽场周边土壤和水中环丙氨嗪和三聚氰胺污染情况调查

通过现场采样,采集到上海、广东以及江苏10家畜禽场周边199份环境样本,并利用超高效液相色谱-串联质谱对采集到的土壤样品和水样中的环丙氨嗪和三聚氰胺残留量进行分析。分析结果表明,畜禽场周围环境中存在一定程度的三聚氰胺污染,环丙氨嗪的污染情况则相对较轻;随着土层的加深,土层中三聚氰胺残留呈下降趋势。经调查,三聚氰胺和环丙氨嗪在环境中的分布与环丙氨嗪在畜禽场的使用形式和周期密切相关;污染情况还存在地域差别,江苏省和上海市畜禽场周围的三聚氰胺污染情况较广东省严重。     

冬小麦?夏玉米体系磷效率对塿土磷素肥力的响应

【目的】 研究塿土区冬小麦?夏玉米轮作体系磷肥利用效率 (PUE) 和土壤肥力 (磷素) 的关系,可以界定土壤磷素的最佳管理范围及合理施磷量,为实现作物高产和减少磷素损失提供理论依据。 【方法】 采取塿土长期定位试验5个不同磷素水平的土壤,有效磷含量依次为3.90 (F1)、15.00 (F2)、23.60 (F3)、35.70 (F4) 和50.00 (F5) mg/kg进行盆栽试验,供试作物为小麦‘小偃22’和玉米‘郑单958’。每个磷素水平土壤上设置5个施磷量 (P₂O₅ 0、30、60、90、120 kg/hm2)。作物成熟后,收获地上部所有植株,晒干、脱粒后测定地上部生物量、籽粒产量,籽粒和秸秆样品粉碎后测定其含磷量。作物收获后均匀采集盆内土样约50 g/盆,风干并混匀后分别过1 mm和0.15 mm筛,测定土壤速效磷和全磷含量。计算冬小麦?夏玉米种植体系磷肥利用效率与土壤磷素水平的关系。 【结果】 F1土壤增施磷肥可显著提高小麦和玉米的籽粒产量,与P0相比,所有施磷处理小麦增产52.2%～119.7%、玉米增产94.7%～212.7%;F2、F3、F4和F5土壤磷肥增产效果不显著。经过两季作物种植,与P0相比,F2土壤施磷60 kg/hm2、120 kg/hm2和F5土壤施磷120 kg/hm2显著提高了全磷含量,其他磷水平土壤全磷含量无显著变化;F1、F2、F3、F4和F5土壤施磷处理的土壤速效磷含量分别增加了?4.08%～434.69%、26.49%～112.77%、6.74%～48.24%、4.07%～43.65%和?4.84%～28.29%。冬小麦磷肥利用效率 (PUE) 与土壤Olsen-P之间呈显著的正相关关系 (P < 0.05),P30、P60、P90和P120线性关系决定系数分别达到0.996、0.899、0.760和0.820。夏玉米PUE在P30下随土壤磷素水平的提高呈二次抛物线形式增加,据此可得出在Olsen-P为12.32 mg/kg时PUE达到100%,当土壤速效磷为33.63 mg/kg时PUE达到最大值155.24%;在P60、P90和P120时,PUE随土壤Olsen-P含量上升而直线增加,Olsen-P分别达到12.22 mg/kg、16.64 mg/kg和14.39 mg/kg后维持在一个水平。整个冬小麦?夏玉米体系PUE随土壤速效磷的变化趋势和夏玉米类似,冬小麦 (P30) 和夏玉米 (P30) 总施磷量为P ₂O₅ 60 kg/hm2时,可算出土壤速效磷为17.97 mg/kg时PUE达到100%;当速效磷达到40.11 mg/kg时,PUE达到最大值131.51%。在同一磷素水平土壤上,随施磷量增加,小麦和玉米PUE均显著降低,尤其是施磷量高于60 kg/hm2后。 【结论】 关中塿土区冬小麦?夏玉米体系,小麦季土壤速效磷应大致控制在17～40 mg/kg范围内,玉米季土壤速效磷控制在13～34 mg/kg范围内进行管理;整个冬小麦?夏玉米体系将土壤速效磷大概控制在17～40 mg/kg范围内,总推荐施磷量为P₂O₅ 60～120 kg/hm2为宜。      

冬小麦-夏玉米体系磷效率对鴥土磷素肥力的响应

【目的】研究鴥土区冬小麦-夏玉米轮作体系磷肥利用效率(PUE)和土壤肥力(磷素)的关系,可以界定土壤磷素的最佳管理范围及合理施磷量,为实现作物高产和减少磷素损失提供理论依据。【方法】采取鴥土长期定位试验5个不同磷素水平的土壤,有效磷含量依次为3.90 (F1)、15.00 (F2)、23.60 (F3)、35.70 (F4)和50.00(F5) mg/kg进行盆栽试验,供试作物为小麦‘小偃22’和玉米‘郑单958’。每个磷素水平土壤上设置5个施磷量(P2O5 0、30、60、90、120 kg/hm~2)。作物成熟后,收获地上部所有植株,晒干、脱粒后测定地上部生物量、籽粒产量,籽粒和秸秆样品粉碎后测定其含磷量。作物收获后均匀采集盆内土样约50 g/盆,风干并混匀后分别过1 mm和0.15 mm筛,测定土壤速效磷和全磷含量。计算冬小麦-夏玉米种植体系磷肥利用效率与土壤磷素水平的关系。【结果】F1土壤增施磷肥可显著提高小麦和玉米的籽粒产量,与P0相比,所有施磷处理小麦增产52.2%～119.7%、玉米增产94.7%～212.7%;F2、F3、F4和F5土壤磷肥增产效果不显著。经过两季作物种植,与P0相比,F2土壤施磷60 kg/hm~2、120 kg/hm~2和F5土壤施磷120 kg/hm~2显著提高了全磷含量,其他磷水平土壤全磷含量无显著变化;F1、F2、F3、F4和F5土壤施磷处理的土壤速效磷含量分别增加了-4.08%～434.69%、26.49%～112.77%、6.74%～48.24%、4.07%～43.65%和-4.84%～28.29%。冬小麦磷肥利用效率(PUE)与土壤Olsen-P之间呈显著的正相关关系(P 0.05),P30、P60、P90和P120线性关系决定系数分别达到0.996、0.899、0.760和0.820。夏玉米PUE在P30下随土壤磷素水平的提高呈二次抛物线形式增加,据此可得出在Olsen-P为12.32 mg/kg时PUE达到100%,当土壤速效磷为33.63 mg/kg时PUE达到最大值155.24%;在P60、P90和P120时,PUE随土壤Olsen-P含量上升而直线增加,Olsen-P分别达到12.22 mg/kg、16.64 mg/kg和14.39 mg/kg后维持在一个水平。整个冬小麦-夏玉米体系PUE随土壤速效磷的变化趋势和夏玉米类似,冬小麦(P30)和夏玉米(P30)总施磷量为P2O5 60 kg/hm~2时,可算出土壤速效磷为17.97 mg/kg时PUE达到100%;当速效磷达到40.11 mg/kg时,PUE达到最大值131.51%。在同一磷素水平土壤上,随施磷量增加,小麦和玉米PUE均显著降低,尤其是施磷量高于60 kg/hm~2后。【结论】关中鴥土区冬小麦-夏玉米体系,小麦季土壤速效磷应大致控制在17～40 mg/kg范围内,玉米季土壤速效磷控制在13～34 mg/kg范围内进行管理;整个冬小麦-夏玉米体系将土壤速效磷大概控制在17～40 mg/kg范围内,总推荐施磷量为P2O5 60～120 kg/hm~2为宜。     

土壤中石油类污染物的化学氧化去除研究

用H2O2氧化处理柴油重度污染土壤,研究了土壤初始含油量、H2O2投加量、土壤pH值以及催化剂等的影响.结果表明,室温条件下向油污土壤中直接投加氧化剂的修复方法可行;H2O2的经济添加量为400 ml/kg土,低含油(20000 mg/kg)污土的去除率可达70.0%以上,高含油(50000 mg/kg)污土的去除率可达96.0%以上:pH 5～8范围内土壤介质对该法的应用影响不大;如用芬顿试剂处理高含油(50000 mg/kg))污土,H2O2只需100 ml/kg土或200 ml/kg土,就能达到85.0%以上的去油效果.     

利用多功能针式过滤器快速检测油菜和苹果中68种农药及代谢物残留

针对国家农产品质量安全例行监测涉及的68种农药及代谢物,采用基于QuEChERS方法的多功能针式过滤器快速净化,建立了油菜和苹果中68种农药及11种代谢物的多残留快速检测方法,其中48种农药及8种代谢物采用液相色谱-串联质谱(LC-MS/MS), 20种农药及3种代谢物采用气相色谱-串联质谱(GC-MS/MS)进行检测分析。结果表明,目标物在0.01～0.2 mg/L范围内线性关系良好,相关系数为0.990 5～0.999 9。在0.01～0.2 mg/kg的添加水平下,油菜的回收率为60.3%～119%,相对标准偏差为0.58%～19.4%(n=5);苹果的回收率为60.5%～118%,相对标准偏差为0.71%～19.2%(n=5)。方法检出限为0.005～0.01 mg/kg,定量限为0.01～0.05 mg/kg。将本方法应用于实际样品检测,发现油菜中虫螨腈、吡虫啉、啶虫脒、氯氰菊酯、腐霉利有检出,残留量为0.012～0.21 mg/kg;苹果中戊唑醇、氯氟氰菊酯、氯氰菊酯、腐霉利、联苯菊酯有检出,残留量为0.01～0.19 mg/kg,表明所建立的方法具有良好的实用性。     

高效液相色谱法测定土壤中均三氮苯类除草剂

采用高效液相色谱法测定土壤中7种均三氮苯类除草剂:西玛津、阿特拉津、扑灭通、莠灭净、扑灭津、扑草净、去草净。用乙腈或甲醇:乙腈(3:7v/v)在索氏提取器上提取土壤中的7种均三氮苯类除草剂,提取液经旋转蒸发,氮吹浓缩,中性氧化铝小柱净化,再次氮吹浓缩后,高效液相色谱二极管阵列检测器检测,外标法定量,检测波长为224nm。实验结果表明该方法的变异系数在1.24%～6.83%之间,平均回收率在95.0%～106.9%之间,检出限为0.84～2.07μg/kg。该方法是分析土壤中均三氮苯类除草剂农药的一种较为理想的方法。     

阿灭净在菠萝与土壤中的残留及消解动态研究

采用气相色谱(GC-NPD)分析技术测定除草剂阿灭净在菠萝与土壤中的残留及消解动态结果表明,GC-NPD方法的最小检出量为0.0232ng,菠萝及土壤的最小检出浓度分别为0.002mg/kg和0.005mg/kg,GC-NPD方法回收率分别为87.23%~92.10%和88.80%~93.77%。喷施阿灭净80%WP4800g(a.i/)hm2,处理检测出菠萝与土壤中原始沉积量分别为0.1448~0.1646mg/kg和3.3318~3.5536mg/kg,消解半衰期分别为29.17~29.45d和25.75~30.68d,按阿灭净用量4800g(a.i/)hm2施药菠萝1次,间隔期为10d,菠萝果实残留量2年分别为0.1646mg/kg和0.1448mg/kg,参照欧共体的MRL值0.2mg/kg,按上述阿灭净剂量方法施用菠萝是安全的。     

苯噻酰草胺水解产物的鉴定及其检测方法的建立

基于飞行时间高分辨质谱,鉴定了苯噻酰草胺的水解产物,并通过优化QuEChERS方法提取溶剂的pH,结合高效液相色谱串联三重四极杆质谱技术建立了同时检测稻田中苯噻酰草胺及其代谢产物的方法。结果表明,2-苯并噻唑氧乙酸和N-甲基苯胺是苯噻酰草胺主要的水解产物;以含1%甲酸的乙腈(v/v)作为2-苯并噻唑氧乙酸和苯噻酰草胺的提取溶剂,含0.5%氨水的乙腈(v/v)作为N-甲基苯胺的提取溶剂,通过使用XSelect HSS T3色谱柱实现了苯噻酰草胺及其代谢物的分离,苯噻酰草胺、 2-苯并噻唑氧乙酸和N-甲基苯胺分别在0.1～100μg/L、 1～500μg/L和1～500μg/L的范围内线性关系良好,定量限分别为0.1μg/kg、 1.0μg/kg和1.0μg/kg,目标化合物在4种不同基质中回收率为81.0%～116.9%,基质效应为-18.7%～10.5%,相对标准偏差≤13.9%,所建方法可为检测苯噻酰草胺及其代谢物在稻田环境中的残留提供技术支撑。     

Application and fate of Cyromazine in a closed-cycle hydroponic cultivation of bean (Phaseolus vulgaris L.)

The fate of cyromazine applied via the nutrient solution (20, 40, and 60 mg of active ingredient per plant) in a closed-cycle soilless cultivation of bean with zero discharge of effluents was traced in both the recycled drainage solution and the plant tissues for 99 days. The insecticide was applied once, 15 days after planting (16 days prior to the first harvest). In addition to cyromazine, the residues of melamine, its metabolite, in the drainage solution and plant tissues were also regularly determined during the 99 days. The two higher application doses induced toxicity symptoms on the leaves of the bean plant. The maximum cyromazine levels were measured 8 days after application in the drainage solution (17-46 mg l(-1)), 16 days in the roots (1.1-2.4 mg kg(-1) fresh weight [f. wt.]) and the vegetative shoot (4.5-9.5 mg kg(-1) f. wt.), and 24 days after application in the pods (2.6-4.1 mg kg(-1) f. wt.). However, the cyromazine residues in pods were clearly below the maximum acceptable levels for bean. The half-life of cyromazine in the drainage solution ranged from 16 to 19 days for the three doses. The melamine residues in the drainage solution and in the roots reached a concentration peak 16 days after cyromazine application, whereas in the vegetative shoot and the pods they were constantly increasing over the 99 days after application. Nevertheless, the melamine residues were constantly much lower than those of cyromazine, although on the last sampling day (99) they tended toward convergence. Cyromazine proved to be highly persistent, as indicated by the remarkably high residues measured in both the drainage solution and the plant tissues, even 99 days after application. Nevertheless, the application of cyromazine via the nutrient solution to beans grown in closed-cycle hydroponic systems at doses not exceeding 20 mg per plant seems to be safe with respect to both phytotoxicity and residue levels in the edible pods.     

Analytical method for the determination of cyromazine and melamine residues in soil using LC-UV and GC-MSD

A method is reported for the determination of cyromazine and melamine residues in soil. Soil samples are extracted twice via mechanical shaking, each time with 70% acetonitrile/30% 0.050 M ammomium carbonate for 30 min. An aliquot portion of the pooled extracts is subjected to strong cation exchange (SCX) purification on AG 50W-X4 resin. Final analysis is accomplished using liquid chromatography-ultraviolet (LC-UV) detection at a wavelength of 214 nm. Confirmatory analyses can be performed using gas chromatography-mass selective detection (GC-MSD) in the selected ion monitoring (SIM) mode. The limit of detection (LOD) is 2.5 ng injected and the limit of quantification (LOQ) is 10 ppb when using LC-UV for the analysis of N-cyclopropyl-1,3,5-triazine-2,4, 6-triamine (cyromazine) and 1,3,5-triazine-2,4,6-triamine (melamine). The LOD is 0.050 ng injected and the LOQ is 10 ppb when using GC-MSD for confirmatory analyses. The mean procedural recoveries were 97 and 95% and the standard deviations were 16 and 11% for cyromazine and melamine, respectively (n = 24), when using LC-UV. The mean procedural recoveries were 107 and 92% and the standard deviations were 9.9 and 16% for cyromazine and melamine, respectively (n = 29), when using GC-MSD. The method validation study was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160. The method also passed an Independent Laboratory Validation (ILV) as per U.S. EPA FIFRA Subdivision N.     

Determination of acequinocyl and hydroxyacequinocyl on fruits and vegetables by HPLC-DAD

A method for determining residues of the new reduced-risk pesticide acequinocyl and its deacetylated derivative hydroxyacequinocyl on fruits and vegetables (grapes, lemons, pears, and tomatoes) by HPLC is described. The pesticides were extracted from the fruits and vegetables with hexane and ethyl acetate solution (1:1, v/v), determined by HPLC-DAD at 250 nm and confirmed by LC/MS. No cleanup was necessary. This method is characterized by recoveries (0.01-4 mg/kg) > 77%, while the coefficient of variation was determined to be less than 11%. The limit of quantitation for both acequinocyl and hydroxyacequinocyl was 0.01 mg/kg for all matrixes.     

Rapid and sensitive determination of phenol in honey by high-performance liquid chromatography with fluorescence detection

The objective of this research was to develop a novel high-performance liquid chromatographic (HPLC) method involving a simple sample preparation procedure for the rapid, low-cost, and sensitive quantitation of phenol in honey at levels of regulatory and practical importance. After proper dilution of honey with water, the samples were analyzed by a gradient HPLC system, using a reversed-phase column with fluorescence detection at excitation and emission wavelengths of 270 and 300 nm, respectively. The eluents applied were water-acetonitrile-85% orthophosphoric acid (10:10:0.01, v/v/v) and water-85% orthophosphoric acid (20:0.01, v/v). The retention time of phenol was found to be 14.1 min, and the limit of quantitation for phenol in honey was set at 5 microg/kg. Overall recovery was 98%. The proposed method has been successfully applied to real sample analysis.     

Determination of acetamiprid,imidacloprid, and nitenpyram residues in vegetables and fruits by high-performance liquid chromatography with diode-array detection

Determination of 3 neonicotinoid insecticides, nitenpyram, imidacloprid, and acetamiprid, was studied. Vegetables and fruits were extracted with acetonitrile. The crude extract was passed through a weak anion-exchange cartridge (PSA). The effluent was subjected to silica gel cartridge. Imidacloprid and acetamiprid were eluted with 10 mL of 4:6 (v/v) acetone/hexane, followed by nitenpyram with acetone (20 mL). Pesticides were determined by HPLC with a C-18 column and diode-array detection system. Imidacloprid and acetamiprid were recovered at about 90% at the spike levels with 0.2 and 2 mg/kg in cucumber, potato, tomato, eggplant, Japanese radish, and grape. Nitenpyram was recovered at 64-80%. Relative standard deviations were less than 10% throughout all the recovery tests. In the residue analysis, agriculturally incurred pesticides at 0.08-0.14 mg/kg were designated with UV spectra compared with respective reference standards.     

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) method extension to quantify simultaneously melamine and cyanuric acid in egg powder and soy protein in addition to milk products

As a consequence of the adulteration of infant formulas and milk powders with melamine (MEL) in China in 2008, much attention has been devoted to the analysis of MEL [and cyanuric acid (CA)] in dairy products. Several methods based on high-performance liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry (LC-MS/MS), nuclear magnetic resonance (NMR), or Raman spectroscopy have been described in the literature. However, no method is available for the simultaneous determination of MEL and CA in other raw materials, which are considered as high-risk materials for economically motivated adulteration. The present paper reports the results of an interlaboratory-based performance evaluation conducted with seven laboratories worldwide. The purpose was to demonstrate the ability of a cleanup-free LC-MS/MS method, originally developed for cow's milk and milk-powdered infant formula, to quantify MEL and CA in egg powder and soy protein. Limit of detection (LOD) and limit of quantification (LOQ) were 0.02 and 0.05 mg/kg for MEL in egg powder and soy protein, respectively. For CA, LOD and LOQ were 0.05 and 0.10 mg/kg in egg powder and 1.0 and 1.50 mg/kg in soy protein, respectively. Recoveries ranged within a 97-113% range for both MEL and CA in egg powder and soy protein. Reproducibility values (RSD(R)) from seven laboratories were within a 5.4-11.7% range for both analytes in the considered matrices. Horwitz ratio (HorRat) values between 0.4 and 0.7 indicate acceptable among-laboratory precision for the method described.     

Simple and efficient method for the estimation of residues of flubendiamide and its metabolite desiodo flubendiamide

An analytical method was standardized for the estimation of residues of flubendiamide and its metabolite desiodo flubendiamide in various substrates comprising cabbage, tomato, pigeonpea grain, pigeonpea straw, pigeonpea shell, chilli, and soil. The samples were extracted with acetonitrile, diluted with brine solution, and partitioned into chloroform, dried over anhydrous sodium sulfate, and treated with 500 mg of activated charcoal powder. Final clear extracts were concentrated under vacuum and reconstituted into HPLC grade acetonitrile, and residues were estimated using HPLC equipped with a UV detector at 230 lambda and a C18 column. Acetonitrile/water (60:40 v/v) at 1 mL/min was used as mobile phase. Both flubendiamide and desiodo flubendiamide presented distinct peaks at retention times of 11.07 and 7.99 min, respectively. Consistent recoveries ranging from 85 to 99% for both compounds were observed when samples were spiked at 0.10 and 0.20 mg/kg levels. The limit of quantification of the method was worked out to be 0.01 mg/kg.     

壤和堆肥中四环素类抗生素的检测方法优化及其在土壤中的降解研究

在对土霉素（OTC）、四环素（TC）和金霉素（CTC）3 种四环素类抗生素的高效液相色谱（HPLC）检测分析方法以及在土壤和堆肥中的提取方法进行改进和优化的基础上,采用该方法进行了 3 种抗生素在土壤中的降解试验。结果表明,选用 Agilent Eclipse XDB-C8（4.6150 mm,5 m）色谱柱,以 0.01 mol/L草酸/乙腈/甲醇（79/10.5/10.5,v/v/v）为流动相,紫外检测波长 268 nm,流速 1.0 mL/min,进样量 5 L,采用外标法定量,可使 3 种四环素类抗生素在 20 min 内全部洗脱并达到基线分离; 在 0~10 mg/L 范围内,抗生素浓度与峰面积呈显著的线性关系,相关系数（r）均 0.999。土壤和堆肥样品中的 OTC、TC 和 CTC可用1 mol/L NaCl/0.5 mol/L 草酸/乙醇（25/25/50,v/v/v）混合溶液提取,其回收率在 76.0%~92.5% 之间。加入到土壤中的抗生素在 25℃下避光培养 49 d 后,在壤土和红土中的降解率分别是 67%~72% 和 36%~46%,对应的半衰期分别为 2630 d 和 4675 d,说明抗生素在壤土中比红土中容易降解。此外,3种抗生素在壤土中的半衰期没有显著性差异,而在红土中 CTC 和 TC 的降解速率显著高于 OTC。     

Determination of ETU in tomatoes and tomato products by HPLC-PDA: evaluation of cleanup procedures

An HPLC-PDA method for the determination of ethylenethiourea (ETU), the main degradation product of the organic fungicides ethylene bis(dithiocarbamate)s (EBDCs), in tomatoes and tomato products is reported. Solid-matrix liquid-liquid (l-l) partitioning and separatory funnel l-l partitioning for the cleanup were examined. The effect of salt addition, pH, and phase ratio on analyte recovery at the cleanup step was studied. It was found that solid-matrix l-l partitioning afforded higher precision and more selective separation of the analyte. According to the method proposed, the samples were extracted with methanol/water (3:1, v/v) and cleaned up on an Extrelut 20 column. ETU was eluted with dichloromethane and separated on a reversed phase HPLC column. For tomato products with degrees Brix > 20 further purification through silica cartridge was adopted. The method was validated over the following ranges of concentrations: 0.01-0.5 mg/kg for tomatoes, 0.01-0.1 mg/kg for tomato juice, and 0.05-0.25 mg/kg for tomato paste. The accuracy (recoveries > 70%) and the precision obtained (%RSD < 10%) were satisfactory.     

不同种类与浓度的阴离子对菠菜镉吸收的影响

通过盆栽试验,研究了不同种类与浓度的阴离子（Cl-, SO42-）以及不同镉（Cd）水平对菠菜镉吸收的影响。结果表明,随着土壤中Cd浓度的增加,菠菜中的Cd浓度也随之增加。施Cd 1 mg/kg处理,菠菜中Cd浓度是对照的11～17倍;而施Cd 5 mg/kg处理,菠菜中Cd 浓度是对照的10～43倍。增施Cl- 可使土壤溶液中镉浓度增加,进而提高菠菜中镉浓度。施Cl- 5与10 mmol/kg,菠菜中Cd浓度分别为对照的1.45倍与2.31倍。施SO42-处理,则会降低菠菜中Cd浓度。施SO42- 5 mmol/kg ,Cd浓度仅为对照的0.77倍。土壤溶液中的Cd浓度与Cl- 浓度呈显著正相关。