QuEChERS提取法在农产品农药残留检测中的应用进展

食品中的农药残留检测长期以来一直是一项艰巨的挑战,其杂质干扰多,残留含量低,传统的提取方法常常因为无法将杂质分离而影响检测结果。由于食品中杂质种类众多,农药的种类繁多且理化性质各异,新型农药日益涌现,所以对样品的前处理提出了更高的要求。近年来,QuEchERs（Quick,Easy,Cheap,Effective,RuggedandSafe）作为一种新型的提取方法,由于具有快速、简单、廉价、有效、可靠、安全的特点,成为国内外广泛采用的样品前处理新技术,在多种农药、医药、兽药的气相或液相色谱分析中已经得到广泛应用。本文就国内外对QuEChERS法在各类食品以及其他动植物性农产品的农药残留检测中的应用和方法的改进进行了综述,并对QuEChERS法在今后农药残留检测的应用前景以及发展方向进行了展望。     

Distribution and incorporation mode of the herbicide MCPA in soil derived organo-clay complexes

The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH^?, BBr₃, RuO₄, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.     

Physical,chemical and biological behaviour of fumigants on cottonseed

Fumigation is required to protect cottonseed in storage and pre-shipment from insect pests and/or microorganisms. Fumigation of cottonseed with carbon disulphide (CS₂), carbonyl sulphide (COS), ethanedinitrile (C₂N₂), ethyl formate (EF), methyl bromide (MB) and phosphine (PH₃) showed that >85% of the fumigants disappeared within 5?h of exposure. COS maintained >20?mg L^–1 for 24?h. After 1?day of aeration, 75%–85% of the absorbed COS and MB and 20%–40% of the absorbed CS₂, EF and PH₃ were released from treated cottonseed. The fumigant residues were reduced by 80% for COS, 50% for EF or MB and 25% for CS₂ after 1?day of aeration. After 13?days of aeration, fumigant residues were reduced by 95% for MB, 65% for EF, 55% for CS₂ and to natural levels in the COS residue. Carbon disulphide, COS, PH₃, EF and C₂N₂ had no effect on the germination of cottonseed, but germination was reduced to 50% by MB. COS has potential as a fumigant for control of insect pests in cottonseed because it dissipates quickly and does not negatively impact germination. On the other hand, MB appears to strongly absorb and requires an extended period for residues to dissipate, and it negatively impacts germination.     

碘化钾碱性高锰酸钾法测定化学需氧量有关问题的释疑

最常见的化学需氧量(COD)的测定方法是铬酸钾法和高锰酸钾法。但用上述两种方法测定废水中COD时易受到氯离子的干扰。为此,提出了用“碘化钾碱性高锰酸钾法”消除氯离子干扰的机理。对碘化钾高锰酸钾法验证的结果表明,该方法适用于测定油气田和炼化企业高氯、低氯废水的COD。求出用碘化钾高锰酸钾法与铬酸钾法测定的COD比值,可将碘化钾碱性高锰酸钾测定法的CODOH.KI换算成铬酸钾法的CODCr值来衡量水体的有机物污染情况及判断废水是否达到排放标准。     

Risk Assessment and Management of Contamination of Eels (Anguilla Spp.) By Persistent Xenobiotic Organochlorine Compounds

Contaimination of anguillid eels by organochlorine pesticides and PCBs is reviewed using a risk assessment-management approach. Quantitative structure-activity relationships, biomonitoring of body residues and field and laboratory studies demonstrate hazards and risks of persistence; organic carbon binding, sediment transport and sinks; volatility, aerial transport and deposition; hydrophobicity/lipophilicity, bioaccumulation, bioconcentration and dietary biomangification. Risks of acute narcotic toxicity are generally lower than those of chornic effects. Cause-effect relationships and critical loadings are, however, unclear. Critical environmental and body residue levels to protect eels and animal and humans consumption must be formulated and interpreted with caution. Risks for eels at different life-stages and in different habitats are compared with respect to routes of uptake, elimination, bioaccumulation and biomagnification. It is concluded that organochlorine contamination has not been a major cause of recent declines in eel recruitment. the use of eels in biomonitoring and biomarker studies are recommended. Appropriate methodologies and uses in risk assessment and management are discussed.     

A simple and convenient empirical survey method with a soil electrical conductivity meter for incineration residue-derived soil contamination

To facilitate field surveys for identifying areas of incineration residue-derived soil contamination, a simple and convenient method with a soil electrical conductivity meter was examined. First, the leaching test specified by Notification No. 13 of the Ministry of the Environment, 1973, was conducted on 506 samples of 11 types of wastes and compost, and the relationship between the concentrations of toxic elements [total Hg (T-Hg), Cd, Pb, Cr⁶⁺, and As] and values of electrical conductivity (EC) was examined. The results showed that bottom ash and fly ash were wastes with high EC values and that these wastes indicated higher levels of toxic elements. Second, an estimation method for the soil EC value of contaminated soil (ECc) was proposed based on the EC values of noncontaminated soil, and its usefulness was examined. The results of field surveys conducted at sites whose soils were suspected of contamination by dioxins and other pollutants derived from incineration residues showed that the contaminated spots and areas were identified by using ECc values. Moreover, comparison of the elemental contents of soils in terms of Cr, Ni, Zn, Na, K, Ca, Fe, Mn, and others, in addition to the above-mentioned toxic elements (excluding Cr⁶⁺), with those of the potential sources of pollution was verified to be effective for identifying the source of soil contamination.     

不同水热炭化条件处理青霉素菌渣制备生物炭

为了考察不同水热炭化条件处理青霉素菌渣制备的生物炭特征,采用菌渣中分别添加氯化钠、柠檬酸和硝酸铁为添加剂和分别设置不同温度的方法,分析不同温度、不同添加剂对水热炭化产物特征的影响。结果表明, 在210 ℃时,各种样品的干重产率较高。对于水热产物结构,RNa温度最佳为210 ℃;RAc和RFe最佳温度为180 ℃。在180 ℃时,RH产物孔径平均当量直径最大为3.61 μm;RNa、RAc、RFe变化不大,分别为3.08、3和3.16 μm,变化幅度小于0.2 μm;在210 ℃时,对照产物孔径平均当量直径大于180 ℃时产物为3.94 μm;而RNa为2.99 μm,RAc、RFe孔径依次减小,为别为2.33 μm和1.84 μm。添加剂对产物孔径平均当量直径有影响,而添加剂种类影响不大;温度变化对RNa产物孔径平均当量直径影响不大,对RFe产物影响最明显。     

The fate of the herbicide propanil in plants of the littoral zone of the Three Gorges Reservoir (TGR), China

The anti-seasonal hydrology with 30 m water fluctuations in the Three Gorges Reservoir(TGR) of China attracts growing environmental and ecological concerns. We investigated the biotransformation of the herbicide propanil in plants dominating in the littoral zone of the TGR by applying the ~(14)C-ring-labeled herbicide into non-aseptic hydroponic plant systems(Cynodon dactylon, Nelumbo nucifera and Bidens pilosa), aseptic plants(Lemna minor and Lemna gibba) and cell suspension cultures(C. dactylon and L. minor).(1) Propanil absorbed in plants of the hydroponic systems was(12.46 ± 1.63)% of applied radioactivity(AR)(C. dactylon),(52.36 ± 6.38)%(N. nucifera) and(76.55 ± 6.07)%(B. pilosa), respectively. The ~(14)C-residues in the plant extractable fractions and the corresponding media were confirmed by radio-Thin Layer Chromatography(TLC), radio-High Performance Liquid Chromatography(HPLC) and Gas Chromatography-Electron Ionization Mass Spectrometry(GC–EIMS) as propanil,3,4-dichloroaniline(DCA) and N-(3,4-dichlorophenyl)-β-D-glucopyranosylamine(Glu-DCA).(2)About 8% of AR was taken up by both aseptic plants, from which 7.0% of AR was extracted and identified also as propanil, DCA and Glu-DCA.(3) Concerning cell suspension cultures,(39.22 ±9.39)% of AR was absorbed by C. dactylon after 72 hr, whereas the accumulated ~(14)C-propanil by L.minor cell suspension culture amounted to(65.04 ± 1.72)% after 7 days. The identified compounds in cell cultures are consistent with those in the tested plants. Most of the pesticide residues in the intact plants were un-extractable, which are recognized as the end of the detoxification process. We therefore consider these plants as suitable for the phytoremediation of the herbicide propanil in the TGR region.     

干法半干法脱硫灰升温过程中二氧化硫的逸出规律

通过改变焙烧温度、焙烧时间和通气流量等条件,研究了干法半干法脱硫灰中二氧化硫的逸出规律。结果表明:850℃~1050℃,二氧化硫的逸出量随着温度的升高而增加,大约由0.15mg/g增加到0.5mg/g;脱硫灰焙烧1h后二氧化硫逸出量比焙烧10min后增加最多为0.047mg/g,因此焙烧10min二氧化硫基本全部逸出;在通气量0.6L/min~0.9L/min的范围内,二氧化硫逸出量随着通气流量的增加而增加,不同焙烧时间时的增加量都约为0.062mg/g,然后趋于平缓,最后基本不受通气流量的影响;计算得出二氧化硫最大排放浓度为101.4mg/m3,远远低于国家标准的规定800mg/m3,因此在脱硫灰渣的再利用中不会对环境造成危害。     

Assessment of Pesticide Residues in Two Arable Soils from the Semi-Arid and Subtropical Regions of China

The residues of 31 chlorinated hydrocarbons (CHCs), 25 chlorophenols (CPs), 30 organophosphorus (OP) and pyrethroid (PRT) in two arable soils from the semi-arid and subtropical regions of China were assessed. Data obtained indicate that the main compounds of CHC pesticide residues in the semi-arid soil were 4,4′-DDE (25.3 ng/g) and β-HCH (14.1 ng/g), which totally accounted to about 90% of total CHC residues detected. The total content of CHC residues detected in the subtropical soil was only 3.1 ng/g, of which approximately 50% was β-HCH. However, the total content of CP residues in both of the soils was about 11 ng/g. In the semi-arid soil, only parathion-methyl amongst the 30 compounds of OP and PRT residues was detected (32.5 ng/g), whilst malathion and parathion-methyl (8.7 and 17.7 ng/g, respectively) detected in the subtropical soil. Based on these results, it was suggested the environmental risk of pesticide residues ranked in an order as CHCs (mainly as 4,4′-DDE, β-HCH) > OP (parathion-methyl) > CPs for the semi-arid soil, and as OPs (parathion-methyl and malathion) > CPs > CHCs (β-HCH) for the subtropical soil.