Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Distribution and ecological risk of organochlorine pesticides and polychlorinated biphenyls in sediments from the Mediterranean coastal environment of Egypt

Organochlorine contamination in the Mediterranean coastal environment of Egypt was assessed based on 26 surface sediments samples collected from several locations on the Egyptian coast, including harbors, coastal lakes, bays, and estuaries. The distribution and potential ecological risk of contaminants is described. Organochlorine compounds (OCs) were widely distributed in the coastal environment of Egypt. Concentrations of PCBs, DDTs, and chloropyrifos ranged from 0.29 to 377 ng g⁻¹ dw, 0.07 to 81.5 ng g⁻¹ dw, and below the detection limit (DL) to 288 ng g⁻¹ dw, respectively. Other organochlorinated pesticides (OCP) studied were 1–2 orders of magnitude lower. OCP and PCBs had higher concentrations at Burullus Lake, Abu Qir Bay, Alexandria Eastern Harbor, and El Max Bay compared to other sites. OCP and PCB contamination is higher in the vicinity of possible input sources such as shipping, industrial activities and urban areas. PCB congener profiles indicated they were derived from more than one commercially available mixture. The ratios of commercial chlordane and heptachlor metabolites indicate historical usage; however, DDT and HCHs inputs at several locations appear to be from recent usage. The concentrations of PCBs and DDTs are similar to those observed in sediments from coastal areas of the Mediterranean Sea. Ecotoxicological risk from DDTs and PCBs is greatest in Abu Qir Bay, Alexandria Harbor, and El-Max Bay.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

Residues of organochlorine pesticides in surface soils from college school yards in Beijing, China

Organochlorine pesticides (OCPs) have been a major environmental issue, attracting much scientific concern because of their nature of toxicity, persistence, and endocrine disrupting effects. Soil samples were collected from ten college school yards in Beijing in 2006 and analyzed to determine fifteen OCPs. Dichlorodiphenyltrichloroethanes (DDTs) were found to be the main pollutants, accounting for 93.70% of total OCPs, followed by hexachlorohexanes (HCHs) (2.25%) and hexachlorobenzene (HCB) (1.82%). Content...     

基于固定化AChE的流动注射型酶传感器研究

以固定化鲅鱼脑组织乙酰胆碱酯酶[acetylcholinesterase,AChE(EC 3.1.1.7)]为识别元件,以pH电极为换能器,构建流动注射型AChE酶传感器.该传感器在以磷酸盐缓冲液为载液的条件下具有良好的重现性(RSD=1.427%,n=10)和敏感性,可实现对有机磷化合物的在线监测;对甲基对硫磷具有线性响应的浓度范围为4.29×10-10^-4.29×10^-8mol·L^-1,最低检测限为1.3×10^-     

南四湖沉积物中有机氯农药和多氯联苯垂直分布特征

通过对采集于南四湖湖区的沉积物柱状样品中有机氯农药（OCPs）和多氯联苯（PCBs）同系物的GC-ECD定量分析测定,并结合²¹⁰Pb同位素定年分析,重建了南四湖湖区有机污染物的污染史.结果表明,样品中OCPs、HCHs、DDTs和PCBs的含量范围分别为1.64～17.9、0.66～12.5、0.24～2.99和7.84～42.8 ng·g^-1.柱状沉积物的沉积速率为0.330 cm·a^-1,平均沉积通量为0.237 g·(cm²·a)^-1,所采集的样品沉积时间为1899～2000年.OCPs和PCBs分别在1960和1970年左右出现浓度峰值,随后含量逐渐下降.污染物来源分析表明,HCHs来源于新的工业HCH和林丹2种工业品,HCH和DDT污染主要源于历史上的使用;PCBs主要来自于造纸漂白过程和焚烧炉排放.生态风险评价结果表明,除β-HCH、γ-HCH和艾氏剂3种污染物在14～16　cm附近、对应沉积时间为1960年左右测试数据略高于风险水平低值,其余污染物的所有数据均低于风险水平低值.整体而言,南四湖柱状沉积物中的OCPs和PCBs含量属于低生态风险水平.     

典型持久性有机污染物在翅碱蓬中的分布特征

碱蓬是潮间带的常见优势种群,为了解其在持久性有机污染物从陆域向海洋迁移中所起的作用,利用GC-MS研究了东营和营口潮间带盐沼植物翅碱蓬不同器官及根系土中有机氯农药(OCPs)、多环芳烃(PAHs)、十溴联苯醚(BDE209)和多氯联苯(PCBs)的含量和分布特征.结果表明,4类持久性有机污染物在翅碱蓬中的污染水平依次为ΣPAHsΣOCPsBDE209ΣPCBs(96～1506ng/g、14～577ng/g、1.8～33ng/g和399～2161pg/g).营口潮间带沉积物中OCPs、PAHs和PCBs的污染水平高于东营,但这3类污染物在两地潮间带翅碱蓬叶子中的含量水平相当.OCPs在两地翅碱蓬各器官中的分布相同,即茎根叶,PAHs和PCBs2种污染物受根系土中有机质含量的影响,在翅碱蓬器官中呈现不同的分布.BDE209在东营潮间带的污染水平(19.7ng/g)高于营口(2.36ng/g),在碱蓬器官中呈现不同分布.     

青岛近海沉积物中多环芳烃、多氯联苯和有机氯农药的含量和分布特征

利用气相色谱/质谱方法对青岛近海表层沉积物中多环芳烃(PAHs)、多氯联苯(PCBs)和有机氯农药(OCPs)进行了测定,并分析了PAHs、PCBs和OCPs的分布特征.结果表明,PAHs、PCBs和OCPs的均值分别为684.80、6.87和13.52ng·g-1,含量变化均呈近岸高、远岸低的分布规律.燃料的高温燃烧排放对本研究海域沉积物中PAHs有较大贡献;PCBs主要来源于工业及生活排放,但已受到控制;沉积物中HCHs存在工业和农业双重污染源输入,DDT主要是由于历史上使用农药造成,且在表层沉积物中受到好氧微生物降解.与国内外同类研究结果相比,调查海域沉积物中PAHs、PCBs和OCPs的污染程度及生态风险均处于较低水平.     

荧光桃红-溴化十六烷基三甲基铵检测有机磷农药残留总量

在pH为6.40的B-R缓冲溶液中,荧光桃红与一定浓度的溴化十六烷基三甲基胺发生荧光增强反应,加入有机磷农药后,体系的荧光强度降低,且降低程度与有机磷农药的加入量呈良好的线性关系,建立了用此荧光法来测定有机磷农药残留总量的新方法.在优化试验条件下,线性范围为0.008-0.72 mg·L-1,检出限为0.05 mg·L...     

苏州、无锡和南通城市地表灰尘中的有机氯农药

2009年7月在江苏省南部城市苏州,无锡和南通采集了58个城市地表灰尘样品, 使用加速溶剂萃取、气相色谱质谱法测定了样品中的22种有机氯农药(OCPs).结果表明,样品中有19种OCPs被检出,总OCPs含量为76.6mg/kg.六氯苯(HCB)、总滴滴涕(DDTs)和氯丹是样品中检测出的主要OCPs,检出率分别为100%、100%和82.8%,含量分别为26.8mg/kg(0.432~348mg/kg)、39.6mg/kg(1.95~559mg/kg)和6.17mg/kg(ND~145mg/kg).城市地表灰尘样品与中国城市大气样品中检测出OCPs的种类基本一致,而各化合物之间的比例不同.与郊区农田土比较,地表灰尘中检测出的OCPs种类多且含量高.样品中(DDD+DDE)/DDTs的比值显示地表灰尘中的DDT大部分已经降解.城市地表灰尘中的HCB含量较高,工业污染来源可能性较大,工业污染源释放的HCB已经通过大气传输影响到了城区.城市地表灰尘中的反式-氯丹与顺式-氯丹的比值平均为1.94,表明城市中仍有新近使用氯丹的现象.