通过式固相萃取/超高效液相色谱-串联质谱法测定蔬菜中18种农药残留

建立了超高效液相色谱-串联质谱(UPLC-MS;MS)快速测定蔬菜中18种农药残留的方法.样品经乙腈提取后,经Oasis PRiME HLB固相萃取柱净化,采用ACQUITY UPLC HSS T3 C18(50 mm×2.1 mm,1.8μm)色谱柱进行分离,以0.1%甲酸水溶液和乙腈作为流动相进行梯度洗脱.采用电喷雾电离源、正离子模式下以多反应监测(MRM)进行定性和定量分析.结果表明,18种农药在0.5—50μg·L^-1范围内线性关系良好(r2>0.995),方法最低检出限为0.4—1.5μg·kg^-1,最低定量限为1.4—5.0μg·kg^-1.在韭菜、芹菜、番茄、白菜基质中,5、10、50μg·kg^-1添加水平下的加标回收率为60.2%—126.9%,相对标准偏差(RSD)为0.4%—21.6%(n=3).     

Study of the levels of N‐methylcarbamate pesticides in waters of the river Huelva

A study on the levels of N‐methylcarbamate pesticides and some degradation products in waters of the river Huelva was carried out. This river constitutes the main water supply of the city of Seville at the south west of Spain with a population of almost one million inhabitants. N‐methylcarbamates were extracted from the water by using C‐18 solid phase cartridges. High performance liquid chromatography with UV detection was used to carry out the determinations. Residues of carbaryl, methiocarb sulphoxide and α‐naphthol were found in some of the analysed water samples.     

可吸入尘中苯并（a）芘超声提取的高效液相色谱测定法

本文介绍一种简便、快速的可吸入尘中苯并(a)茈高效液相色谱测定方法.本法仅需5mL乙腈,超声处理10min即可完成提取过程.提取液离心后,上清液可直接进行HPLC分析.色谱条件:反相C18柱,用乙腈/水梯度洗脱,紫外检测器,λ=254nm.方法的最小检出量10~(-10)g.回收率95%,变异系数4、3%.此方法可用于大气可吸入尘中Bap的监测.     

Coexisting sediments and suspended particles change the sorption of lindane and ciprofloxacin in waters

The real behavior of water organic contaminants such as pesticides and pharmaceuticals is not well known because research experiments usually simplify the conditions by studying the sorption of a pure compound on a single solid. However, in natural waters, biofilms, suspended particles, and sediments are solid substances that coexist, and thus may change the contaminant fate. Therefore, we studied here the sorption of lindane and ciprofloxacin by three single-solid and three double-solid sorbents using batch experiments. We also compared the effect of dissolved organic matter (DOM) between single- and double-solid sorption systems. Results show that the sorption quantity of lindane to the double-solid system of suspended particles and sediments is lower, of 0.99 L/g, than the sum of sorption quantity in the single-solid system, of 1.39 L/g. The sorption quantity of ciprofloxacin is higher, of 2.70 L/g, than the sum of sorption quantity in the single-solid system, of 1.90 L/g. These findings are explained by changes in DOM that suppress or promote sorption. To our best knowledge, this is the first study to present evidence that coexisting river solids modify lindane and ciprofloxacin sorption.     

高效液相色谱串联大气压化学电离源质谱(HPLC-APCI-MS)法测定水中三氯生

建立了高效液相色谱串联大气压化学电离源质谱(HPLC-APCI-MS)测定水中三氯生的方法,预处理采用正己烷液液萃取法萃取三氯生,回收率达99.6%;优化的色谱质谱联机分析条件为:检测波长230 nm,流动相乙腈/水(75∶25),离子源APCI源,负离子模式;该分析方法能在5 min内实现对水中三氯生的定性与定量分析.质量保证(Quality Assurance,QA)与质量控制(Quality Control,QC)研究得出,仪器检测限为0.18μg·L-1,相对标准偏差(relative standard deviations,RSD)为0.59%;空白加标实验回收率为103%,RSD为1.2%;以城市生活污水、河水和自来水为加标基质实验回收率为96.6%—108%,方法检测限为0.26—0.61μg·L-1,RSD为0.28%—0.81%.该方法操作简便,分析方法准确性、精密性与可靠性均较高.     

顶空-固相微卒取-气相色谱测定水体中痕量苯系物

对测定水体中痕量苯系物的顶空-固相微萃取-气相色谱法的固相微萃取条件进行了对比优化,经过对水体中的7种苯系物对比实验,确定了顶空-固相微萃取-气相色谱法的固相微萃取的最佳实验条件为：选用75μmCAR/PDMS萃取涂层,加入与水质量比为40%的氯化钠,于20℃温度下萃取40min,解析3min。方法检出限为0.12～0.19μg/L,相对标准偏差2.0%～3.9%。依据确定的优化条件,用不同类型的水样对优化后的试验条件进行了验证试验,回收率在96.2%～102.0%之间,表明优化后的试验条件适用于多类型水体中痕量苯系物的分析测定。     

Arsenic species in the well water and sediments of the blackfoot disease area in Taiwan

The blackfoot disease (BFD) observed in southwestern Taiwan is due to drinking high arsenic concentrations in well water. This paper presents some results concerning the distributions of arsenic species in water and sediments collected in the BFD (well, river and coastal) area and the background (lake and ocean) area for comparison. The results show that the concentrations of arsenate (870 ± 26 ug/L) and arsenite (70.2 ± 2.6 ug/ L) in well waters, and the contents of arsenic (1640 ug/g) with high percentage of easily reducible (Fe and Mn oxides, 91.7%) and exchangeable and carbonate (4.6%) phases in well sediments were much higher than those in river, lake and coastal samples. Low arsenic (3.46–31.8 ug/g) with high percentages (73.8–97.3%) of detritus and minerals phase with low percentages (0.4–9.8%) of total carbonate and exchangeable phases were found in the river and coastal samples in the BFD area as well as the lake and ocean samples in background area. It might suggest that the higher concentrations of toxic As(III) in well water and arsenic with higher values of easily reducible, carbonate and exchangeable phases in the well sediments, combined with the higher values of dissolved organic carbon, humic and fulvic acids and aromatic carbon as well as the higher fluorescence indensity in the well water are the key factors to cause the BFD in Taiwan.     

同位素内标-高效液相色谱-串联质谱法测定畜禽粪便中6种雌激素

为了研究畜禽粪便中雌激素的污染特征及其环境影响,建立了一种同时提取、分离和检测畜禽粪便中雌酮(E1)、17α-雌二醇(17α-E2)、17β-雌二醇(17β-E2)、雌三醇(E3)、17α-炔雌醇(17α-EE2)和己烯雌酚(DES)共6种雌激素的高选择性和高灵敏性方法——同位素内标-固相萃取-高效液相色谱-串联质谱法。对提取剂、淋洗剂、洗脱剂、色谱分离条件和质谱测定条件等进行了优化。最终的优化方法为:粪便样品加入100 ng同位素内标后,先后用乙腈重复超声提取3次(每次10 mL,每次15 min),离心后合并上清液,旋转蒸发近干再复溶于1 mL甲醇,加7 mL纯水稀释并超声混匀后离心,上清液过0.45μm滤膜后用HLB固相萃取柱净化,经10 mL 15%乙腈水溶液淋洗后,用10 mL的甲醇进行洗脱,氮吹浓缩定容至1 mL,过0.22μm滤膜后测定。用2 mM氟化铵-甲醇为流动相,经TAB色谱柱分离后采用电喷雾离子源和选择反应监测负离子扫描模式进行检测,同位素内标定量。在5、50、200、1000 ng·g^?1加标水平下,6种雌激素的平均回收率为90.2%—103.2%,相对标准偏差为0.09%—9.08%,方法检出限(LOD)和方法定量限(LOQ)分别为0.25—0.95 ng·g^?1和1.00—3.82 ng·g^?1。应用此方法检测了6个猪粪、3个牛粪和3个鸡粪样品中6种雌激素的含量,结果为?1(干质量)。该方法灵敏度高,定量准确且定量范围广,适用于畜禽粪便中6种雌激素的定性定量分析。     

克螨特和霸螨灵及其混剂在水中的光降解

研究了克螨特、霸螨灵在几种水体中的光降解以及 2种农药之间的光敏化或光猝灭效应。结果表明 ,在 3 0 0W高压汞灯光照处理时 (试验试管距光源 8cm) ,克螨特和霸螨灵都极易降解 ,克螨特的光解半衰期为 9.0 6min ,霸螨灵的光解半衰期仅为 1 .4 8min。克螨特在不同水体中的光解率为 :重蒸馏水 >鱼塘水 >河水 >井水 ,霸螨灵的光解率为 :井水 >重蒸馏水 >鱼塘水 >河水 ;2种农药在现采水、过滤水、灭菌水中的光解率依次降低。克螨特和霸螨灵混剂在重蒸馏水中互为光猝灭剂 ,在井水、河水和塘水中霸螨灵对克螨特有极显著的光敏化作用 ,而克螨特对霸螨灵有极显著的光猝灭效应。克螨特、霸螨灵在pH 5和 pH 9缓冲液中光解率比之在 pH 7缓冲液中稍快 ,光猝灭效应也较强烈。在重蒸馏水中太阳光照处理时 ,克螨特和霸螨灵互为光敏剂 ,而高压汞灯下则互为光猝灭剂。     

Organochlorine pesticides and PCBs in sediments from the Yangtse River,China

Organochlorine Pesticides and PCBs pollution levels were determined in sediment samples taken from three sites along the Yangtse River (Nanjing part). The concentrations of various pesticides were in the range of 1.42–8.06 ng/g (t‐HCH), and <0.01–4.12ng/g (t‐DDT), while the concentrations of PCBs were below detection limit at all three sites. The contamination by Organochlorine Pesticides and PCBs in sediments from the Yangtse River was not significant when compared with that reported in the literature from some other countries’ rivers, which may be due to the high flow velocity and water amount of the Yangtse River.     

在线柱浓缩-液相色谱法测定水体中痕量敌草快和百草枯

采用在线柱浓缩-超快速液相色谱联用技术测定水体中痕量百草枯和敌草快.水样无需样品前处理,过滤后即可进样.采用固相萃取小柱富集待测物,以色谱梯度泵完成样品的净化后,利用阀切换技术将待测物反冲至分析柱进行分离,以二极管阵列检测器定量.方法在1.0—20.0μg.L-1范围内线性良好,百草枯和敌草快的线性相关系数分别为0.9997和0.9989.百草枯和敌草快的检出限(S/N=3)分别为0.10、0.12μg.L-1,加标回收率在96.0%—98.0%之间.用所建立的方法测定了水中痕量的百草枯与敌草快的含量,结果令人满意.     

高效液相色谱-荧光检测法同时测定畜禽粪便中4种磺胺类药物残留

建立了高效液相色谱-荧光检测法测定畜禽粪便中4种磺胺药物(磺胺甲基嘧啶(SM1)、磺胺氯哒嗪(SCP)、磺胺邻二甲氧嘧啶(SDM’)、磺胺喹噁啉(SQ))的方法.样品用25 mL甲醇提取3次,合并提取液,浓缩干燥,用0.1 mol.L-1的HCL溶解残渣,经荧光胺衍生化后,用反相C18柱为分离柱,以乙腈∶0.5%乙酸=40∶60(V/V)为流动相进行洗脱,20 min内分离4种药物.在0.05—5.00μg.mL-1范围内,4种磺胺类药物的峰面积与质量浓度的线性关系良好(R2≥0.999),SM1、SCP、SDM’、SQ的定量限(LOQ)分别为2.3、6.3、4.3和9.6μg.kg-1;添加水平为50、100、1000μg.kg-1时,SM1、SCP、SDM’、SQ的回收率分别为74.91%—81.82%、78.45%—91.43%和86.10%—92.88%,RSD小于8.82%.     

Mitigation of agricultural nonpoint-source pesticide pollution in artificial wetland ecosystems

Contamination caused by pesticides in agriculture is a source of environmental poor water quality in some of the European Union countries. Without treatment or targeted mitigation, this pollution is diffused in the environment. Pesticides and some metabolites are of increasing concern because of their potential impacts on the environment, wildlife and human health. Within the context of the European Union (EU) water framework directive context to promote low pesticide-input farming and best management practices, the EU LIFE project ArtWET assessed the efficiency of ecological bioengineering methods using different artificial wetland (AW) prototypes throughout Europe. We optimized physical and biological processes to mitigate agricultural nonpoint-source pesticide pollution in artificial wetland ecosystems. Mitigation solutions were implemented at full-scale demonstration and experimental sites. We tested various bioremediation methods at seven experimental sites. These sites involved (1) experimental prototypes, such as vegetated ditches, a forest microcosm and 12 wetland mesocosms, and (2) demonstration prototypes: vegetated ditches, three detention ponds enhanced with technology of constructed wetlands, an outdoor bioreactor and a biomassbed. This set up provides a variety of hydrologic conditions, with some systems permanently flooded and others temporarily flooded. It also allowed to study the processes both in field and controlled conditions. In order to compare the efficiency of the wetlands, mass balances at the inlet and outlet of the artificial wetland will be used, taking into account the partition of the studied compound in water, sediments, plants, and suspended solids. The literature background necessary to harmonize the interdisciplinary work is reviewed here and the theoretical framework regarding pesticide removal mechanisms in artificial wetland is discussed. The development and the implementation of innovative approaches concerning various water quality sampling strategies for pesticide load estimates during flood, specific biological endpoints, innovative bioprocess applied to herbicide and copper mitigation to enhance the pesticide retention time within the artificial wetland, fate and transport using a 2D mixed hybrid finite element model are introduced. These future results will be useful to optimize hydraulic functioning, e.g., pesticide resident time, and biogeochemical conditions, e.g., dissipation, inside the artificial wetlands. Hydraulic retention times are generally too low to allow an optimized adsorption on sediment and organic materials accumulated in artificial wetlands. Absorption by plants is not either effective. The control of the hydraulic design and the use of adsorbing materials can be useful to increase the pesticides residence time and the contact between pesticides and biocatalyzers. Pesticide fluxes can be reduced by 50–80% when hydraulic pathways in artificial wetlands are optimized by increasing ten times the retention time, by recirculation of water, and by deceleration of the flow. Thus, using a bioremediation method should lead to an almost complete disappearance of pesticides pollution. To retain and treat the agricultural nonpoint-source po a major stake for a sustainable development.     

Suspended solid abatement in a conical fluidized bed flocculator

With the random movement of silica gel beads in a conical fluidized bed, micro-vortices resulting from the fluidization promoted the collision and aggregation of suspended fine kaolin powders. The abatement efficiencies of the suspended fine solids under several hydrodynamic conditions were studied, and a suitable control strategy for operating the conical fluidized bed flocculators was identified. The suspended solids abatement efficiency was found to increase with increasing Camp Number and flocculation time (T), but decreased with the increase of velocity gradient (G) within the range studied in this research (165.1–189.6 s^-1). The abatement efficiencies were all more than 60% at the range of G = 165–180 s^-1 and T = 15–33 s at an initial kaolin solid concentration of 150 mg·L^-1, polymer aluminum chloride dosage of 60 mg·L^-1 and sedimentation time of 20 min. However, the formation of flocs was influenced by the liquid backmixing. Excessive backmixing caused the breakup of flocs and resulted in difficulty for the fine powders to aggregate and sediment to the reactor bottom. The results of the calculated fractal dimension and measured free sedimentation velocity of flocs obtained at different runs showed similar flocs properties, and indicated an easy control strategy for sedimentation of the flocs.     

Adsorption and partition of benzo(a)pyrene on sediments with different particle sizes from the Yellow River

Experiments have been carried out to study the sorption of Benzo(a)pyrene(Bap) on sediment particles from the Yellow River using a batch equilibration technique. Effects of particle size on the adsorption and partition of Bap were investigated with the particle content of 3 g/L. Several significant results were obtained from the study. (1) Isotherms of Bap could be fitted with the dual adsorption-partition model under different particle sizes, and the measured value of the adsorption and partition was in agreement with the theoretical value of the dual adsorption-partition model. (2) When the particle diameter was d ? 0.025 mm, the adsorption was predominant in the sorption of Bap, which accounted for 68.7%–82.4% of the sorption. For the particles with the size of 0.007 mm?d<0.025 mm, the adsorption was predominant when the equilibrium concentration of Bap was 0–8.87 μg/L in the water phase; and the partition was predominant when the equilibrium concentration of Bap was higher than 8.87 μg/L in the water phase. When the particle diameter was d<0.007 mm, the partition was predominant. (3) On the point of particle size, the contribution of adsorption to sorption followed the order: “d?0.025 mm”>“0.007 mm ?d<0.025 mm” >“d<0.007 mm”. (4) The partition coefficients of Bap in solids with different particle sizes were linearly correlated with the organic content, and the K _oc of Bap was about 1.26 × 10⁵ (L/kg).     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.     

Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

内河螺蛳（Margaryamelanioides）对水环境中邻苯二甲酸酯类的富集

为探索内河底栖生物对水环境中PAEs的富集规律,采用气相色谱质谱法定量测定宁波城市内河回龙段水体、底泥、螺蛳肉与壳中DMP、DEP、DIPP、DPP、DBP、BBP、DEHP和DOP的浓度。结果表明研究河域底泥、水样、螺蛳（Margaryamelanioides）肉和螺壳样品主要存在DMP、DBP、DEHP3种PAEs,DMP的平均浓度分别为3．435μg／g、0．023μg／g、1．239μg／g和0．712μg／g,DBP为2．613μg／g、0．484μg／g、6．984μg／g和0．282μg／g;DEHP为13．891μg/g、0．030μg／g、4．938μg／g和0．156μg／g,∑PAEs表现为底泥〉螺蛳肉〉螺壳〉水样。螺蛳肉及螺蛳壳对酯类富集能力分别表现为DEHP〉DBP〉DMP,DMP〉DEHP〉DBP,且螺蛳肉的富集能力明显强于螺蛳壳。螺蛳肉与水样DMP浓度呈显著的正相关,DBP和DEHP不相关;螺蛳壳中3种PAEs均与采样位点水样的PAEs呈显著的相关性;螺蛳肉、螺蛳壳与底泥的PAEs浓度均呈显著的相关性;各位点的螺蛳肉与螺蛳壳富集的3种PAEs浓度均呈显著的正相关。     

Chlorophenol tolerant and degradative bacteria isolated from a river receiving pulp mill discharges

A screening was carried out in a river receiving pulp mill discharges (BioBio river, central Chile) to study the bacterial population able to tolerate and degrade chlorophenols. In four selected stations and at different seasons, water samples were taken from the river. Total bacterial population and the number of chlorophenol tolerant bacteria were counted. Bacterial tolerance to 25, 50, 100, 200 and 400 μg/ml of 2,4‐dichlorophenol (DCP), 2,4,6‐trichlorophenol (TCP) and pentachlorophenol (PCP) was determined. Strains able to tolerate at least 400 μg/ml chlorophenols were found. Eighteen bacterial strains able to use chlorophenols as the sole carbon source were isolated: five of them were Pseudomonas fluorescens, two Alcaligenes sp., one Citrobacter freundii, one Aeromonas sp. and nine unidentified Gram negative bacilli. A good correlation (r ² = 0.758) between the logarithm of DCP tolerant bacteria and the content of adsorbable organic halogen (AOX) at low dilution in the river water was established. Four groups of tolerant bacteria were found: growing on PCP and DCP, growing on PCP and TCP, growing only on PCP and growing only on TCP.     

Paraben-chlorinated derivatives in river waters

This article reports the first identification of paraben-chlorinated derivatives in river water. Parabens are widely used as preservatives in pharmaceuticals and personal care products. Parabens can be easily chlorinated by chlorinated tap water. The resulting chlorinated derivatives might pose a higher potential risk to humans and ecosystems than the corresponding parent parabens. However, the occurrence of such derivatives in rivers remains unknown so far. We studied 23 parabens and their chlorinated derivatives from rivers receiving effluents from sewage treatment plants in Shizuoka city, in the central Pacific region of Japan. The compounds were extracted by solid-phase extraction with a styrene polymer sorbent, trimethylsilyl-derivatized, and then identified by gas chromatography–mass spectrometry. Six chlorinated parabens and their primary degradation products, two chlorinated hydroxybenzoic acids, were found for the first time in river water. Moreover, in river water, chlorinated derivatives preferentially partition into the suspended-solid phase.