Removal,adsorption and desorption of pentachlorophenol (PCP) by filamentous fungi: Rhizopusarrhizus and Cunninghamella elegans in batch system

PCP was, and in some countries still is, one of the most frequently used fungicides and pesticides, specially in wood preservation. The extensive use is correlated with contamination of water and soil and it is detected in several compartments of the food chain.

Some Micromycetes are able to adsorb and degrade PCP, with two mechanisms involved: biosorption (including both adsorption and absorption) and biodegradation.

Our work is focused on the biosorption alone and biodegradation‐biosorption of PCP by respectively denatured and living R.arrhizus and C.elegans fungi.

Living fungi are cultivated in batch system and denaturation is obtained by drying (70°C) and grinding the fungi to a calibrated powder (200–400 μm). Kinetic studies are performed with 10 mg/1 PCP initial concentration. Adsorption capacity is measured at equilibrium concentration as high as about 400 mg/1 PCP.

The results show that: PCP adsorption, for the two fungi, follows a two steps process. R. arrhizus dead and living biomasses are able to bind respectively, 75 and 55% of a 10 mg/1 PCP initial concentration in 1 hour contact time and then 75 and 100% in 96 hours. For C.elegans, 70 and 28% in 1 hour and in 96 hours 70 and 90%, respectively.

The PCP binding by living fungi is higher than non living ones, but with a slower rate.

The maximum PCP adsorption capacity is about 24 mg/g of R.arrhizus dried biomasses and 16 mg/g for C.elegans ones, in 48 hours contact time. Isotherm curves follow the Langmuir model.

Desorption studies with methanol (to reuse biomasses) shows that it is a rapid phenomenon (about 100% in 24 hours for the two fungi).

An industrial and economical process to depollute contaminated water by PCP is possible by using cheap fungal by‐products from fermentation industries.     

Characterization of an adsorbed humin-like substance on an allophanic soil formed via catalytic polycondensation between catechol and glycine, and its adsorption capability to pentachlorophenol

An allophanic soil (AS) catalyzed the formation of dark-colored polymers via polycondensation reactions between catechol and glycine. The organic carbon content of the AS was increased from 0.16% to 1.3%, indicating that some of the dark-colored polymers had been adsorbed to the AS. The characteristics of the dark-colored polymers adsorbed on the AS were similar to those of a humin that is not extractable with an aqueous alkaline solution. Such a humin-like substance (HuLS) was separated from the AS by treatment with a mixture of HF and HCl. The HuLS and humic acid-like substance (HaLS), comprising the acid-insoluble fraction in the reaction mixture, were characterized by elemental analysis, size exclusion chromatography, pyrolysis-GC/MS and ¹³C NMR. However, the structural features of HaLS and HuLS had many points in common. These results suggest that HuLS-AS can be regarded as an organo-clay complex formed by the strong adsorption of HaLS to the AS. The adsorption of pentachlorophenol (PCP) to AS and HuLS-AS was examined at pH 5.5. At this pH, the zeta potential of the HuLS-AS showed a negative value. It would, therefore, be expected that pentachlorophenolate anions would adsorb with difficulty to HuLS-AS because of electrostatic repulsion. Nevertheless, the adsorption coefficient for PCP to HuLS-AS, as estimated by the Freundlich isotherm, was seven times larger than that for AS. These results show that HuLS, when adsorbed on the AS surface, has the capability to enhance the adsorption of PCP.     

气相色谱/质谱法测定水中五氯酚

用GC/MS法测定环境水体和废水中的五氯酚 ,选择乙酸酐作衍生化试剂 ,二氯甲烷为萃取剂 ,比较了不同的衍生pH条件 ,以m/z为 2 6 6的定量特征离子定量 ,获得了较高的灵敏度和选择性     

IMPACT OF FOUR PESTICIDES ON THE GROWTH AND METABOLIC ACTIVITIES OF TWO PHOTOSYNTHETIC ALGAE

The acute toxicity was determined for soil algae Chlorella kesslerei and Anabaena inaequalis, exposed to pesticides lindane, pentachlorophenol (PCP), isoproturon (IPU), and methyl parathion (MP). Toxicity markers included growth inhibition, chlorophyll biosynthesis, and total carbohydrate content, as a function of dose and time. Concentration response functions (EC₅₀) were estimated by probit data transformation and weighted linear regression analyses. Lindane's toxicity to Chlorella increased sharply with time (EC₅₀=7490, 10.3, 0.09 mg L^?1; 24, 48, 72 h), but remained nearly constant through 72 h with Anabaena (8.7?6.7 mg L^?1; 24–72 h). PCP at low concentrations stimulated algal growth and chlorophyll a production, an effect reversed at higher doses. Anabaena was less tolerant of PCP and MP than was Chlorella. The 96-h static EC₅₀ values for Chlorella were: 0.003, 34, 0.05, and 291 mg L^?1 for lindane, PCP, isoproturon, and MP, respectively; for Anabaena, these were 4.2, 0.13, 0.21, and 19 mg L^?1. Carbohydrate production responses were similar to those of cell density (growth) and chlorophyll biosynthesis, with MP having the lowest adverse impact. The overall relative toxicity among the four tested pesticides was: for Chlorella, lindane>IPU?PCP?MP; and for Anabaena, PCP>IPU>lindane>MP. The results confirm that toxicants such as these pesticides may affect individual (though related) species to significantly different degrees.     

Residual congener pattern of dioxins in human breast milk in southern Vietnam

This study evaluated residual congener patterns of dioxin/furan (=PCDD/DF) related to tactical herbicides aerially sprayed over the regions of southern Vietnam through Operation Ranch Hand. The study focused on Cam Chinh (CC) commune, Quang Tri province (an area sprayed with tactical herbicides), and the Cam Phuc (CP) commune, Ha Tinh province (a non-sprayed area). Breast milk samples for analysis were collected in September 2002 and July 2003 from lactating primiparous and multiparous mothers born after the war (<31 years old). We found the levels of each congener in the CC commune were higher than in the CP commune, and determined specificity in the PCDD/DF congener pattern in CC commune samples by cluster analysis. The congener pattern is characterized by higher (the hexa-, the hepta-, and the octa-) chlorinated PCDD/DFs; this appears to be the same profile as that presented by pentachlorophenol (PCP), rather than 2,4,5-trichlorophenoxy acid (2,4,5-T) contaminated with 2,3,7,8-TCDD. A GC/MS study in the 1970s detected the chlorophenols 2,4-di and 2,4,6-trichlorophenol in some Agent Orange samples, which contained, like PCP, a wide variety of PCDD/DF congeners. In this context, it may be expected that certain tactical herbicides contaminated with various chlorophenol impurities, have a unique congener pattern when compared with pure 2,4,5-T formulations.     

五氯苯酚在厌氧颗粒污泥中的吸附研究

在血清瓶中进行的分批实验中,研究了UASB和EGSB反应器厌氧颗粒污泥对五氯苯酚(PCP)的吸附、解吸规律.结果表明,吸附和解吸在接触PCP 2.5 h内达到平衡,吸附和解吸过程都符合Freundich等温方程,PCP的吸附机制为恒定的分配吸附.来自UASB反应器中活的颗粒污泥吸附能力大于灭活的颗粒污泥,Freundich等温方程吸附常数K值分别为0.557 0和0.037 9.UASB反应器颗粒污泥对PCP的吸附能力大于EGSB反应器颗粒污泥,Freundich等温方程吸附常数K值分别为0.557和0.263.     

五氯酚对斜生栅藻的毒性效应研究

以斜生栅藻细胞的生长状况、色素(叶绿素a、叶绿素b、类胡萝卜素)及蛋白质含量的变化作为指标,研究了不同质量浓度的五氯酚(0,0.02,0.05,0.10,0.50,1.00 mg/L)对斜生栅藻(Scenedesmus obliquus)的毒性效应.24,48,72,96和120 h五氯酚对斜生栅藻的EC50分别为0.883,0.283,0.225,0.168和0.192 mg/L.斜生栅藻生长受抑制程度随五氯酚质量浓度增加而加强,当五氯酚的质量浓度超过0.50 mg/L时,斜生栅藻的生长几乎完全受到抑制.染毒96 h的斜生栅藻色素(叶绿素a、叶绿素b、类胡萝卜素)含量以及蛋白质含量随着五氯酚质量浓度的增加呈下降趋势,色素比例失调,色素对五氯酚的敏感程度为:类胡萝卜素＞叶绿素a＞叶绿素b;可溶性蛋白质含量与色素含量的减少呈明显线性相关(r=0.793,n=6).      

Effective synthesis of sulfate metabolites of chlorinated phenols

Chlorophenols are an important class of persistent environmental contaminants and have been implicated in a range of adverse health effects, including cancer. They are readily conjugated and excreted as the corresponding glucuronides and sulfates in the urine of humans and other species. Here we report the synthesis and characterization of a series of ten chlorophenol sulfates by sulfation of the corresponding chlorophenols with 2,2,2-trichloroethyl (TCE) chlorosulfate using N,N-dimethylaminopyridine (DMAP) as base. Deprotection of the chlorophenol diesters with zinc powder/ammonium formate yielded the respective chlorophenol sulfate ammonium salts in good yield. The molecular structure of three TCE-protected chlorophenol sulfate diesters and one chlorophenol sulfate monoester were confirmed by X-ray crystal structure analysis. The chlorophenol sulfates were stable for several months if stored at −20 °C and, thus, are useful for future toxicological, environmental and human biomonitoring studies.     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.