1,10-菲啰啉-全氟辛烷磺酸(PFOS)体系共振光散射法测定痕量镉(Ⅱ)

在pH 6.8 Britton-Robinson(BR)缓冲介质中,镉(Ⅱ)与1,10-菲啰啉(Phen)作用后与全氟辛烷磺酸(PFOS)形成离子缔合物,使体系的共振光散射信号显著增强.最大散射峰位于307.0 nm处,其增强散射信号强度与镉(Ⅱ)的浓度在6.0—342.5 ng·mL-1范围内呈线性关系,据此建立了测定镉(Ⅱ)含量的共振光散射分析方法,检出限(3!)为0.6 ng·mL-1,研究了反应产物的RLS光谱特征,适宜的反应条件和影响因素,考察了共存物质的影响.该方法用于自来水和实验室废水样中镉(Ⅱ)的测定,RSD≤4.4%.     

Effects of perfluorooctane sulfonate on behavioural activity,regeneration and antioxidant enzymes in planarian Dugesia japonica

Perfluorooctane sulfonate (PFOS) is a persistent organic pollutant and has been found to be the predominant perfluorinated chemicals (PFCs) in the environment. In the present study, planarian Dugesia japonica is employed to investigate the toxicity of this compound. The behavioural activity, survival, regeneration and antioxidant enzyme activities of the D. japonica exposed to PFOS were investigated. The results showed that the planarian D. japonica is very sensitive to low concentration pollutants including PFOS and suitable for toxicological bioassays. PFOS has severe toxicity in inducing oxidative stress, regeneration and development toxicity in planarians. The toxicity is indicated by reduced planarian locomotor velocity (pLMV), reduced appearance of auricles in regenerating animals, changed in antioxidant enzyme SOD and CAT activities. The information presented in this study will help elucidating the PFOS-induced toxicity in aquatic organisms.     

废啤酒酵母去除水中重金属镉的作用机理

利用废啤酒酵母为生物吸附材料处理水溶液中的Cd2+.为了考察废啤酒酵母表面官能团在生物吸附过程中的作用,分别对废啤酒酵母进行甲醇、甲醛化学修饰,使其表面的羧基发生酯化反应、胺基发生甲基化反应.同时对反应前后溶液pH值的变化进行了监测.结果表明,酯化反应后,废啤酒酵母吸附Cd2+的能力降低,证实羧基在Cd2+吸附中起到了重要作用;甲基化反应后,废啤酒酵母吸附Cd2+的能力升高,是因为反应后pH值变化使Cd2+发生无机微沉淀作用而去除.表面官能团以及pH升高引起的沉淀对镉去除起重要作用.     

Determination of traces of fluorine,chlorine, bromine,cadmium and lead in plastic materials

This paper describes the quantitative determination of F, Cl, Br, Cd and Pb in plastic materials. The concentration of the elements Cl, Br, Cd and Pb is first semiquantitatively measured by X‐ray fluorescence spectrometry (XRF) directly in the solid sample with a detection limit of approximately 10 μg/g. Afterwards, F and any of the other elements which exceed the limit values for materials which are disposable without special precautions are measured after the digestion of the material. The samples are digested either under pressure in an oxygen atmosphere for F, Cl and Br or under pressure with nitric acid for Cd and Pb. The digestion converts the halides to the anions which are measured potentiometrically (F^‐, Br^‐) or with ion chromatography (Cl^‐). Cd and Pb are measured by graphite furnace atomic absorption spectrometry (GF‐AAS). The determination limits achieved are 20 μg/g for F and Br, 250 μg/g for Cl, 0.01 μg/g for Cd and 0.2 μg/g for Pb, all below the limit values set by current regulations in Switzerland.     

不同部位梧桐生物质炭对水溶液中镉吸附的机理

为了探究梧桐不同部位废弃物所制备的生物质炭(皮、枝、叶)对Cd²⁺的吸附效率和稳定修复的机理,以此为园林废弃物炭化利用在重金属污染修复方面的应用提供科学依据.利用实验室模拟法,通过高温煅烧法制备梧桐不同部位生物质炭,采用元素分析仪、比表面积及孔隙分析(BET)、X射线衍射仪(XRD)、扫描电镜/能谱(SEM/EDS)及衰减全反射红外光谱(ATR-IR)等技术研究不同反应时间、重金属浓度和溶液初始pH条件下生物质炭对Cd²⁺吸附效果的影响,并运用四步萃取法和脱附实验分析生物质炭上Cd²⁺的吸附形态和稳定性.3种生物质炭都在8 h左右达到吸附平衡,最终吸附量依次为树皮炭>枝条炭>叶片炭;溶液初始浓度为0.5—2 g·L^-1时Cd²⁺的吸附量呈增长趋势,在2.5—3g·L^-1时逐渐平缓;生物质炭Cd²⁺吸附量均随着pH的升高而升高,但在pH值为5—8时,吸附的趋势逐渐平稳;树皮炭的酸溶态和非生物利用态的稳定Cd形态要高于枝条炭和叶片炭;比表面积不是影响梧桐生物质炭吸附Cd²⁺的主要影响因素,吸附动力学,ATR,XRD和重金属形态萃取均证实Cd碳酸盐类矿物生成是主导吸附机理;3种生物质炭的脱附量在4 h后逐渐趋于平衡,其中脱附量最大为叶片炭,最小为树皮炭.梧桐不同部位的初始性质对生物质炭吸附Cd²⁺具有明显的影响,其中梧桐皮具备更高的吸附量和重金属稳定形态,并且相比其他种类生物质炭有明显优势.因此,从吸附效果和生产成本的角度,本研究建议以梧桐皮为主,枝条和叶片为辅的生物质炭对重金属Cd进行修复治理.     

Removal,distribution and plant uptake of perfluorooctane sulfonate (PFOS) in a simulated constructed wetland system

• PFOS was removed by soil adsorption and plant uptake in the VFCW. • Uptake of PFOS by E. crassipes was more than that of C. alternifolius. • PFOS in wastewater can inhibit the removal of nutrients. • Dosing with PFOS changed the soil microbial community in the VFCW. A vertical-flow constructed wetland (VFCW) was used to treat simulated domestic sewage containing perfluorooctane sulfonate (PFOS). The removal rate of PFOS in the domestic sewage was 93%–98%, through soil adsorption and plant uptake, suggesting that VFCWs can remove PFOS efficiently from wastewater. The removal of PFOS in the VFCW was dependent on soil adsorption and plant uptake; moreover, the percentage of soil adsorption was 61%–89%, and was higher than that of the plants uptake (5%–31%). The absorption capacity of Eichhornia crassipes (E. crassipes) (1186.71 mg/kg) was higher than that of Cyperus alternifolius (C. alternifolius) (162.77 mg/kg) under 10 mg/L PFOS, and the transfer factor of PFOS in E. crassipes and C. alternifolius was 0.04 and 0.58, respectively, indicating that PFOS is not easily translocated to leaves from roots of wetland plants; moreover, uptake of PFOS by E. crassipes was more than that of C. alternifolius because the biomass of E. crassipes was more than that of C. alternifolius and the roots of E. crassipes can take up PFOS directly from wastewater while C. alternifolius needs to do so via its roots in the soil. The concentration of 10 mg/L PFOS had an obvious inhibitory effect on the removal rate of total nitrogen, total phosphorus, chemical oxygen demand, and ammonia nitrogen in the VFCW, which decreased by 15%, 10%, 10% and 12%, respectively. Dosing with PFOS in the wastewater reduced the bacterial richness but increased the diversity in soil because PFOS stimulated the growth of PFOS-tolerant strains.     

Leaching of metals in buried industrial sludge,spiked with cadmium,chromium and lead. Results of a trial

Sludge resulting from industrial waste water treatment at the industrial area of Patras, Greece, was spiked with cadmium, chromium and lead and entrenched in 4 experimental trenches. Soil from the unsaturated zone and sludge from the trenches were sampled at successive time points over a period of 14 months to monitor the movement of metals. Results showed that 94% of cadmium and 80% of lead but only 32% of chromium migrated from the sludge just 14 months after the entrenchment.

At the end of this time the buried sludge could be considered stabilised, as indicated by the total nitrogen content. Cd content in underlying soil layers at 3 m depth showed an increase in the first 7 months followed by a decrease, afterwards. Soil Pb concentration at 3 and 6 m depth was significantly high, in relation to it's initial concentration 14 months after the entrenchment. Pb and Cd in the soil samples were negatively correlated. It is suggested that lead displaces cadmium in the sediments.     

An assessment of copper,zinc and cadmium contamination and their ecotoxicological effects in O. mediterranea Costa, 1853 (Amphipoda,Talitridae)

This study was conducted to compare metals bioaccumulation in the Talitrid O. mediterranea collected from the banks of Bizerte lagoon. Individuals were exposed to a series of contaminated soil with different concentrations of cadmium, copper, and zinc. Biological and physiological responses were highlighted. Body metals concentrations were measured in the talitrid using flame atomic emission spectrometry. Results showed that after the second week, the mortality increased especially with cadmium exposure, and a mass gain was obtained between weeks for copper and zinc. Furthermore, the concentration factor indicated that O. mediterranea could be considered as a macroconcentrator of copper and zinc. Histopathological analysis showed that the different metals concentrations induced significant changes in the morphology and in the ultrastructural organisation of hepatopancreatic cells. Significant alterations obtained after metals exposure were the increase in the number of the majority cell organelles. Also, heavy metals were present in the form of numerous granules with different size in the cell surface. Furthermore, metals exposure affected the brush border causing the disruption of microvilli filament. Through these results, O. mediterranea could be a good indicator providing measurable responses. It could be an attractive candidate for the biochemical study of heavy metals toxicity in coastal ecosystems.     

Uptake of zinc, cadmium and phosphorus by arbuscular mycorrhizal maize (Zea mays L.) from a low available phosphorus calcareous soil spiked with zinc and cadmium

In a multifactorial pot experiment, maize (Zea mays L.) with or without inoculation with the arbuscular mycorrhizal (AM) fungus Glomus mosseae BEG167 was grown in a sterilized soil spiked with three levels of zinc (0, 300 and 900 mg Zn kg⁻¹ soil) and three levels of cadmium (0, 25 and 100 mg Cd kg⁻¹ soil). At harvest after 8 weeks of growth, the proportion of root length of inoculated plants colonized decreased with increasing Zn or Cd additon, and was 56% in the absence of both metals and was reduced significantly to 27% in the presence of the higher levels of both metals. Mycorrhizal plants had higher biomass than non-mycorrhizal controls except at the highest soil level of Cd. Cadmium had more pronounced effects on plant biomass than did Zn at the levels studied and the two metals showed a significant interaction. The data suggest that mycorrhizal inoculation increased plant growth with enchancement of P nutrition, perhaps increasing plant tolerance to Zn and Cd by a dilution effect. AM inoculation also led to higher soil solution pH after harvest, possibly reducing the availability of the metals for plant uptake, and lowered the concentrations of soluble Zn and Cd in the soil solution, perhaps by adsorption onto the extrametrical mycelium.     

Effect of calcium and magnesium on copper,cadmium, and some essential elements of Indian major carps Labeo rohita (Hamilton) and Catla catla (Hamilton) treated with copper and cadmium

The effect of calcium and magnesium either singly or in combination on accumulation of cadmium and copper in Labeo rohita (rohu) and Catla catla (catla) was investigated in this study under laboratory conditions. The investigation showed that copper accumulation in rohu exposed to 0.25 mg L^?1 of copper for 14 days reduced from 31.0 ± 0.4 mg kg^?1 at no calcium/magnesium treatment to 3.5 ± 0.2 and 2.2 ± 0.1 mg kg^?1, respectively, at 75 mg L^?1 calcium or magnesium treatment. The copper level in catla exposed to 0.20 mg L^?1 of copper for 14 days reduced from 5.7 ± 0.1 mg kg^?1 at no calcium/magnesium treatment to 3.4 ± 0.2 and 3.3 ± 0.1 mg kg^?1, respectively, at 300 mg L^?1 calcium or magnesium treatment. The cadmium accumulation in rohu exposed to 0.20 mg L^?1 of cadmium for 14 days reduced from 1.7 ± 0.1 mg kg^?1 at no magnesium treatment to 1.4 ± 0.1 mg kg^?1 at 120 mg L^?1 magnesium treatment. The cadmium accumulation in catla exposed to 0.20 mg L^?1 of cadmium for 14 days reduced from 0.8 ± 0.2 mg kg^?1 at no magnesium treatment to 0.6 ± 0.2 mg kg^?1 at 80 mg L^?1 magnesium treatment. Copper and cadmium treatments also reduced some essential microelements of rohu and catla. Both the fishes restored these elements at different levels of calcium and magnesium.     

梯度薄膜扩散技术(DGT)与传统化学方法评估黑麦草吸收Cd的对比

为研究不同方法评估黑麦草吸收Cd的效果,采集了16个不同理化性质实际Cd污染土壤,盆栽试验种植黑麦草,采用梯度薄膜扩散技术(DGT)测定黑麦草根际土Cd的生物有效性,并与离心法采集土壤溶液、乙酸(HAc)和乙二胺四乙酸二钠(EDTANa2)3种传统提取方法所提取土壤有效态Cd含量进行比较,研究其与黑麦草地上部和地下部Cd含量的相关关系.结果表明,DGT提取的土壤有效态Cd含量与黑麦草中Cd含量的相关性显著高于化学提取法.运用多元统计分析研究土壤pH、阳离子交换量(CEC)、有机质(OM)和土壤颗粒组成等理化指标的影响,提取出两种主成分因子,建立了多元回归模型.第一主成分与OM和黏粒(clay)之间呈显著相关,定义为土壤中影响重金属生物有效性的"有机指标",第二主成分则与土壤pH和CEC相关程度较高,定义为土壤中影响重金属生物有效性的"无机指标".研究表明,第二主成分显著影响了3种化学方法构建的预测模型,而DGT技术综合了两种主成分对土壤有效态Cd含量的影响,所构建的模型几乎不受土壤基本理化性质的影响,说明DGT分析法是一种预测黑麦草吸收Cd的较好方法.     

分散液液微萃取-石墨炉原子吸收光谱法测定环境水样中的痕量镉

建立了分散液液微萃取分离富集一石墨炉原子吸收光谱法测定环境水样中痕量镉的新方法。以二乙基二硫代氨基甲酸钠为螯合剂、四氯化碳为萃取剂、丙酮为分散剂,详细考察YpH值、螯合剂质量分数、萃取剂体积、萃取时间等因素的影响。在优化的实验条件下,方法对水样中镉的检出限为4．2ng-L^-1,线性范围是20-300ng-L^-1,测定结果的相对标准偏差为3．5％,富集倍数达103。将建立的方法应用于三种实际环境水样中镉的检测,加标回收率在92％-108％范围内。本方法具有灵敏、准确、快速、环保的特点,是一种分析水样中痕量镉的较好方法。     

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.     

五氟苯甲酰氯衍生色谱法分析水体中痕量羟基多溴联苯醚

以五氟苯甲酰氯(PFBCl)作为衍生化试剂,气相色谱-电子捕获检测器(Gas chromatography-electron capture detector,GC-ECD)为检测手段,建立了水体中痕量羟基多溴联苯醚(Hydroxylated polybrominated diphenyl ethers,简称OH-PBDEs)的酰基化衍生-GC/ECD检测方法.通过实验讨论了衍生化缓冲溶液、衍生化时间以及衍生后萃取溶液异辛烷的用量对检测结果的影响,确定了最佳的衍生化条件.在最佳的衍生化条件下,4-OH-BDE 42、4’-OH-BDE 49、6-OH-BDE 47、2’-OH-BDE 68和6’-OH-BDE 99的衍生化产物均获得了良好的分离度和色谱响应值.本方法的仪器检出限为0.02—0.14 pg,方法检出限为0.61—4.67 pg.L-1,标准曲线线性相关系数的范围为0.9973—0.9996,相对标准偏差均小于10%.3种采自大连市不同地区环境水样的加标回收率检测结果表明,所建立的分析方法适于水体中痕量OH-PBDEs的检测.     

节杆菌P-1和红球菌J-5降解PVA特性的比较研究

对节杆菌P-1和红球菌J-5降解聚乙烯醇(PVA)的特性进行了比较研究.结果表明,P-1菌在PVA浓度小于1000mgL-1时,PVA降解效率均达到80%以上;J-5菌在PVA浓度为2000mgL-1时,PVA降解效率达到70%.用生产废水进行试验,P-1菌对低浓度PVA废水的处理效率比J-5菌高10%左右;P-1菌受温度的影响小于J-5菌;P-1菌的废水处理效果比J-5菌稳定;分段使用J-5菌与P-1菌处理高浓度的PVA废水具有很好的处理效果,出水能达到国家排放标准.图7表1参9     

水体和甘蓝及土壤中毒死蜱残留检测方法

研究运用不同的样品前处理方式,在装配火焰光度检测器的气相色谱(GC-FPD)上检测,建立了有机磷杀虫剂毒死蜱在水样、土壤和甘蓝中的残留测定方法.研究表明,不同样品中的毒死蜱残留采用本文中介绍的前处理方法是可行的,用石油醚盐析提取和净化水样中毒死蜱,采用丙酮振荡提取甘蓝中毒死蜱,选用索氏提取法提取土壤中毒死蜱,并经液液分配净化后,采用OV-101大口径毛细管柱(30 m×0.53 mm×1.0μm),在装配火焰光度检测器(FPD和磷滤光片)的气相色谱上测定.该分析方法下,毒死蜱的保留时间为1.74 min,线性范围在1.0×10-11—1.0×10-8g之间,其线性相关系数为0.9998,最小检出量为2.0×10-12g.在设定的较低添加浓度的条件下,毒死蜱在水样、土壤与甘蓝上的添加回收率为80%—120%,变异系数均小于5%.该分析方法灵敏、准确、操作简便,适合水样、甘蓝和土壤中低浓度毒死蜱的残留检测.     

乳化剂OP和邻菲啰啉存在下硫氰酸钾分光光度法测定土壤有效铁和植物中的铁

在硫酸介质中，在非离子表面活性剂乳化剂ＯＰ和邻菲啉共同存在下，铁（Ⅲ）与硫氰酸钾形成红色配合物，其最大吸收波长为５２２ｎｍ，表观摩尔吸光系数为２．０７…１０￣４Ｌ／ｍｏｌ．ｃｍ，铁（Ⅲ）含量在０—５０μｇ／２５ｍｌ范围内符合比耳定律．该法操作简便、快速．选择性好，应用于土壤有效铁和植物中铁的测定．结果令人满意．     

中空纤维膜辅助离子液体液相微萃取-高效液相色谱法测定环境水体中的水杨酸

分别以l-辛基-3-甲基咪唑六氟磷酸离子液体([C8MIM][PF6])和三辛基氧化膦(TOPO)作为萃取剂与辅助萃取剂,建立了中空纤维膜辅助的两相液液微萃取-高效液相色谱测定环境水体中水杨酸(Salicylicacid,SA)的新方法.通过对中空纤维膜种类、萃取剂、供体相体积、供体相pH、离子强度和萃取时间相关参数进行优化,获得了较高的富集倍数(1653倍).方法的检出限为0.1μg.L-1,线性范围为0.5—1000μg.L-1.方法对实际样品的加标回收率为89.6%—102.4%,可应用于环境水体中痕量SA的测定.     

脱氧雪腐镰刀菌烯醇、黄曲霉毒素B_1和玉米赤霉烯酮对秀丽隐杆线虫的联合毒性研究

脱氧雪腐镰刀菌烯醇(DON)、黄曲霉毒素B_1(AFB_1)和玉米赤霉烯酮(ZEN)是最为常见的粮食真菌毒素,易共存于谷物产品和动物饲料中,而目前对其联合毒性的研究较少,且研究结果并不完全一致。为探究DON、AFB_1和ZEN的联合毒性作用,本论文以秀丽隐杆线虫(C.elegans)为模型,分别评估了毒素混合物AFB_1+DON、AFB_1+ZEN、DON+ZEN和AFB_1+DON+ZEN对C.elegans的生长发育(体长)和生殖能力(产卵量)的毒性作用,并用Chou-Talalay模型来判定毒素混合物的相互作用类型。研究表明,AFB_1、DON和ZEN单独染毒C.elegans时,其毒作用强弱为AFB_1ZENDON。联合染毒时,AFB_1+DON对C.elegans产生协同作用,而DON+ZEN则产生拮抗作用;AFB_1+ZEN对体长(24 h)和产卵量的毒作用随着暴露浓度的增加,由弱拮抗变为协同作用,而在毒素暴露48 h后,对线虫的生长发育呈协同作用;AFB_1+DON+ZEN除在EC50-24 h和EC75-24 h时对体长产生明显的毒性增强作用外,其他普遍表现出拮抗作用。由此表明,DON、AFB_1和ZEN对C.elegans的联合毒性作用与剂量和时间相关。     

Determination of pesticides in apples,grapes and apple juice from a Kosovo market by gradient liquid chromatography with tandem mass spectrometry

Apple, grape, and apple juice were analyzed for pesticides using a multireaction mode (MRM) method in samples taken from a Kosovo market. With this method it was possible to analyze about 100 pesticides in the ESI mode. In these samples some types of pesticides were found, but most of them did not exceed the maximum tolerance levels. In apple samples, six pesticides were detected but only three of them were in sufficient quantitites. Dimethoat was below the limit, while acephate and imazalil exceeded the limit. In grape and apple juice samples, all of pesticides which were found did not exceed the maximum tolerable limits.