6种硝基苯化合物对海洋生物的急性毒性研究（Study on the Acute Toxicity of Six Nitrobenzenes to Marine Organisms）

为研究硝基苯化合物对海洋生物的毒性,选择了6种代表性硝基苯化合物对小球藻(Chlorella vulgaris)、黑鲷(Sparus macrocep)幼鱼和螠蛏(Siliqua minima)幼体进行了急性毒性实验,获得了这些化合物对这些生物体的急性毒性数据及环境安全浓度.实验结果表明:2,4-二硝基甲苯、2,4-二硝基氯苯、2,4-二氯硝基苯和邻二硝基苯对小球藻48h半数抑制浓度(EC50)分别为0.50、0.21、2.44和0.10mg·L-1,毒性顺序为邻二硝基苯(剧毒)>2,4-二硝基氯苯(剧毒)>2,4-二硝基甲苯(剧毒)>2,4-二氯硝基苯(高毒).2,4-二硝基氯苯、邻二硝基苯、2,4-二硝基甲苯、2,4-二氯硝基苯、对硝基苯胺和硝基苯对黑鲷幼鱼的96h半数致死浓度(LC50)分别为0.14、0.15、4.45、1.37、11.52和5.71mg·L-1,其安全浓度分别为:0.001、0.002、0.04、0.01、0.12、0.06mg·L-1,毒性顺序为2,4-二硝基氯苯(剧毒)>邻二硝基苯(剧毒)>2,4-二氯硝基苯(高毒)>2,4-二硝基甲苯(高毒)>硝基苯(高毒)>对硝基苯胺(中毒).2,4-二硝基氯苯、2,4-二硝基甲苯、2,4-二氯硝基苯、邻二硝基苯、硝基苯和对硝基苯胺对幼蛏的96h LC50分别为0.39、13.20、3.45、15.56、86.90和148.87mg·L-1,安全浓度分别为:0.004、0.13、0.03、0.16、0.87、1.49mg·L-1,毒性顺序为2,4-二硝基氯苯(剧毒)>2,4-二氯硝基苯(高毒)>2,4-二硝基甲苯(中毒)>邻二硝基苯(中毒)>硝基苯(中毒)>对硝基苯胺(低毒).     

大气飘尘中硝基多环芳烃的高效液相色谱分析

叙述了用高效液相色谱分析大气飘尘中硝基多环芳烃化合物的方法。对硅胶柱层析预分离、硝基多环芳烃的还原反应、液-液萃取分离、液相色谱条件和响应线性范围进行了研究。在所选的荧光检测波长下,1-硝基芘和2-硝基芴的最小可测量约为20×10~(-12)g.在国内首次测定了大气飘尘样品中的1-硝基芘含量,两种试样的测定值分别为0.11和1.4ug/1000m~3。     

快速溶剂提取-高效液相色谱-二极管紫外阵列/荧光串联法同时测定土壤中18种多环芳烃

建立了快速溶剂(ASE)提取,高效液相色谱-二极管紫外阵列/荧光串联法测定土壤中18种多环芳烃.通过选择净化小柱和仪器条件的优化,实现了18种多环芳烃组分的完全分离及高灵敏度检测,该方法二极管紫外阵列(PDA)检测器和荧光(RF)检测器检出限分别为0.04—0.6μg·kg-1和0.002—0.07μg·kg-1;4种浓度水平(PDA检测器:0.5μg、2μg;RF检测器:0.02μg、0.05μg)土样加标回收率稳定在82.8%—122%之间,RSD为1%—5%之间.     

10种多氯联苯和16种有机氯农药的分离与检测

建立了反相高效液相色谱(RP-HPLC)和毛细管气相色谱-电子捕获检测器(GC-ECD)分离-检测10种多氯联苯(PCB10)和16种有机氯农药(OCP16)分析方法,优化了影响RP-HPLC分离PCB10和OCP16的影响因素,如流动相、流速和紫外吸收波长等色谱条件,PCB10和OCP16混合液经RP-HPLC分离后的2个洗脱馏分样品,前处理后,用毛细管GC-ECD测定,结果表明,RP-HPLC分离PCB10和OCP16,除CB-28和CB-52与有机氯农药没有分离开外,其它8种多氯联苯与16种有机氯农药可以完全分离开;可以用RP-HPLC分离制备PCB10和OCP16的标准溶液,其最低制备浓度均为0.010 ng·ml-1.     

加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱法(HPLC)测定土壤中青霉素钠

建立了一种加速溶剂萃取(ASE)-固相萃取(SPE)-高效液相色谱(HPLC)测定土壤中青霉素钠的简单、快速的方法.样品以超纯水为提取溶剂,50℃提取温度为ASE提取条件参数;HLB型固相萃取柱富集净化:6.0mL 5%甲醇淋洗、4.0mL乙腈-甲醇(1∶1)洗脱;高效液相色谱-紫外检测器(HPLC-PDA)测定,检测波长λ=191.1nm,柱温30℃,流动相为乙腈-0.1%甲酸/水(1∶1),采用等梯度洗脱程序,取得较好的检测分离效果.对0.5、2.0、8.0mg·kg-1等3个不同添加浓度水平的青霉素钠平均加标回收率范围为73.1%—89.7%,回收率相对标准偏差RSD范围为1.1%—2.9%(n=5),检出限可达235.0μg·L-1.结果表明,该方法操作简单,快速,准确度和精密度均符合质量控制要求,能够满足环境土壤样本中痕量青霉素钠检测分析的要求.     

碳黑中的硝基多环芳烃分析

本文叙述了碳黑中致突变性硝基多环芳烃的分析方法,用不同溶剂萃取碳黑样品表明,氯苯具有较高的提取效率,并对预分离、高效液相色谱条件的选择、检测器波长的确定和响应曲线等进行了讨论。应用本分析方法在某种工业碳黑中检出了3-硝基-9-芴酮。样品色谱峰的定性经与标准样品的色谱保留时间和紫外光谱图进行了对照确认。     

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.     

固相萃取-高效液相色谱法同时测定自来水中氯代多环芳烃和多环芳烃

建立了自来水中6种氯代多环芳烃和15种多环芳烃的固相萃取-高效液相色谱荧光检测分析方法.500 mL水样过C18固相萃取柱富集,经6 mL的50%甲醇水溶液淋洗,10 mL二氯甲烷-正己烷(1∶1)洗脱.目标化合物经色谱柱(SUPELCOSILTMLC-PAH柱,150 mm×4.6 mm,5μm)分离后,荧光检测,外标法定量.结果表明,21种目标化合物在线性范围内线性关系良好,相关系数均大于0.999;目标化合物的加标回收率为70%—98%,相对标准偏差(RSD) 0. 6%—8. 8%;方法的检出限(LOD,S/N=3)为0. 3—5. 0 ng·L~(-1),定量限(LOQ,S/N=10)为1.1—16.7 ng·L~(-1).方法简便快速,可用于自来水中氯代多环芳烃和多环芳烃的检测.     

高效液相色谱法测定土壤中农药灭多威的含量

采用甲醇超声萃取-高效液相色谱-紫外检测器的检测方法测定土壤中灭多威。色谱柱,采用依利特ODS25μm(4.6mm×250mm);淋洗液,采用V(乙腈)∶V(水)=25∶75;检测器,采用紫外,检测波长为235nm,灭多威在0.05~3mg/L范围内,其质量浓度与峰面积呈良好的线性关系(r=0.9998)。检测限0.002mg/kg,精密度RSD=1.15%,加标平均回收率为94.5%。本方法快速、简便、准确,便于普及。首次在国内建立了土壤中农药灭多威的检测方法,对保证食品安全和加强环境保护都有着重要的意义。     

1-硝基芘与苯衍生物共存对斜生栅藻的联合毒性

本文研究了1-硝基芘和硝基苯、苯酚、苯胺、甲苯四种苯的衍生物对斜生栅藻生长抑制的EC_(50)(96h)分别为0.1824mg·l~(-1),36.5164mg·l~(-1),219.0027mg·l~(-1),45.1689mg.l~(-1)和72.3172mg·l~(-1);并进一步研究了它们的联合毒性效应,得出硝基苯、苯酚、苯胺、甲苯和1-硝基的联合效应相加指数AI分别为0.3776,-1.0792,1.5523,-0.7481.相应的效应增加系数依次为1.3776,1/2.0792,2.5523,1/1.7481,硝基苯、苯胺与1-硝基芘混合显示协同作用.而苯酚、甲苯与1-硝基芘混合则显示拮抗作用.     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983-6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC--graphite, activated carbon, and diesel soot--to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H(2)S. All three types of BC enhanced DNT and DBP reduction. H(2)S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.

     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.     

2,4-二硝基甲苯与共存化合物对发光菌的联合毒性

对2,4-二硝基甲苯与共存化合物对发光菌联合毒性的测定结果表明:2,4-二硝基甲苯与邻二硝基苯共存时,对发光菌的联合毒性为协同作用:分别与三种苯的氨基衍生物共存时.联合毒性为拮抗作用,这种拮抗作用与取代基数目、空间位阻等因素有关     

鲤鱼对三种硝基芳族化合物的摄取、释放和生物富集

用第二松花江水和鱼体中多次检出的三种硝基芳族化合物来分别测定鲤鱼体中的生物富集系数（ＢＣＦ），摄取和释放动力学参数，以及在肌肉、肠、肝和鳃等组织中的分布。试验在半静态条件下进行。硝基芳族化合物在鲤鱼体内的释放可用双区一级动力学模型很好地描述。鲤鱼对２，４－二硝基甲苯和对硝基氯苯的富集过程中发现有未知的代谢产物生成。     

硝基苯类、氯酚类化合物对金鱼的急性毒性研究

研究了硝基苯类和氯酚类化合物对鲤科金鱼(Carasscas auratus)的急性毒性.结果显示:①硝基苯类化合物随硝基数目在苯环上的增加,其急性毒性增加.②氯酚类化合物的急性毒性随苯环上氯原子数目的增加而增加.通过实验为定量评估和预测同类型化合物的生物急性毒性提供了参考依据.     

Insect cell-based impedance biosensors: a novel technique to monitor the toxicity of environmental pollutants

Cell biosensors are currently emerging as novel, sensitive techniques to monitor the toxicity of environmental pollutants. Here, we have developed electric cell-substrate impedance sensing (ECIS) for on-line monitoring of the behavior of insect cells. Cells were cultured on a microarray of eight small gold electrodes, deposited on the bottom of tissue culture wells. Upon inoculation, cells showed a tendency to drift downward and attached to the gold surface precoated with the protein Concanavalin A to accelerate the cell attachment. The impedance increased because the cells acted as insulating particles to restrict the current flow. The resulting impedance, a coordination of many biological reactions within the cell, was continuously monitored in real-time to reveal information about cell spreading and micromotion. As the cell behavior was sensitive to external chemicals, the applicability of ECIS for inhibition assays was demonstrated with HgCl₂, 2,4,6-trinitrotoluene (TNT), 2-amino 4,6-dinitrotoluene (2-ADNT) and 1,3,5-trinitrobenzene (TNB). Electronic Publication     

紫羊茅根中铜结合肽的分离和纯化

利用１次ＳｅｐｈａｄｅｘＧ５０凝胶过滤和２次ＱＡＥＳｅｐｈａｄｅｘＡ２５离子交换层析的方法,从最后６ｄ用ＣｕＣｌ２处理（ρ＝２０ｍｇ／Ｌ）、２０ｄ龄的紫羊茅（Ｆｅｓｔｕｃａｒｕｂｒａｃｖ．Ｍｅｒｌｉｎ）根中分离纯化了１个铜结合肽（ＣｕＢＰ２ａ）,该肽在ＳｕｐｅｒｄｅｘＰｅｐｔｉｄｅＨＲ１０／３０预装柱的ＦＰＬＣ凝胶过滤中在λ２５４ｎｍ处只出现一个峰,经分子量标准曲线估计,其Ｍｒ约为１４００,在ＤｅｌｔａＰａｋＣ１８的反相ＨＰＬＣ中,在λ２５４ｎｍ处也只有１个紫外吸收峰值,这都说明该肽已经达到了较高的的纯度．通过光谱分析,发现该肽的最大紫外吸收值在２４８．１ｎｍ处．对Ｃｕ结合物在植物体内的存在状态进行了讨论．     

Fenton oxidation of 2,4- and 2,6-dinitrotoluene and acetone inhibition

The performances and kinetic parameters of Fenton oxidation of 2,4- and 2,6-dinitrotoluene (DNT) in water-acetone mixtures and explosive contaminated soil washing-out solutions were investigated at a laboratory scale. The experimental results show that acetone can be a significant hydroxyl radical scavenger and result in serious inhibition of Fenton oxidation of 2,4- and 2,6-DNT. Although no serious inhibition was found in contaminated soil washing-out solutions, longer reaction time was needed to remove 2,4- and 2,6-DNT completely, mainly due to the competition of hydroxyl radicals. Fenton oxidation of 2,4- and 2,6-DNT fit well with the first-order kinetics and the presence of acetone also reduced DNT’s degradation kinetics. Based on the comparison and matching of retention time and ultraviolet (UV) spectra between high performance liquid chromatography (HPLC) and standards, the following reaction pathway for 2,4-DNT primary degradation was proposed: 2,4-DNT → 2,4-dinitro-benzaldehyde → 2,4-dinitrobenzoic acid → 1,3-dinitrobenzene → 3-nitrophenol.     

Nitropyridoindoles—Formation,characterization and mutagenicity

Nitration of pyridoindoles (β‐carbolines) was carried out using different nitration methods and structural assignments of these nitro compounds were made using different spectroscopic techniques. The mutagenic activity of these nitro derivatives was studied using Salmonella typhimurium strains TA 98 NR and TA 100 NR in the absence as well as in the presence of S‐9 mix. Only trinitro derivatives were found to be highly mutagenic to strain TA 98 NR.