The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB- and HBC- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several ne...The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB- and HBC- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several new low-lying electroinc states are found, and the linear triplet structures are found to have the lowest energy. For the anions, the 2 ∑+ states are lower in energy than the 2Π states. For HCB, the 3Π state is 15.38kcal·mol-1 more stable than the 3∑- state, and for HBC the 3Π is 2.51kcal·mol-1 below the 3∑- state at the first order configuration interaction (FOCI) level. The barriers of the conversion of HBC(3Π) to HCB(3Π), HBC(1△(1A1)) to HCB(1A’C3) and HBC(1△(1A2)) to HCB(1A"C3) are 23.21, 12.97 and 21.09kcal·mol-1,respectively. The activation energies of the conversion of HBC-(2∑+) to HCB(2∑+) and HCB-(2Π) to HBC-(2Π) are 18.13 and 25.88kcal·mol-1, respectively. A symmetry breaking phenomenon is observed in several states. The harmonic vibrational frequencies of the neutral molecules and the anions are also reported to provide information for the possible experimental observation of these species.展开更多
Decomposition of hexachlorobenzene(HCB)was investigated over several metal oxides(i.e.,MgO,CaO,BaO,La2O3,CeO2,MnO2, Fe2O3,and Co3O4)supported on Al2O3,which was achieved in closed system at a temperature of 300°C...Decomposition of hexachlorobenzene(HCB)was investigated over several metal oxides(i.e.,MgO,CaO,BaO,La2O3,CeO2,MnO2, Fe2O3,and Co3O4)supported on Al2O3,which was achieved in closed system at a temperature of 300°C.Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents.The decomposition effciency of different catalysts for this reaction depends on the nature of the metal oxide used,and Al2O3 supported La2O3 was found to be the most active one.Pe...展开更多
Hexachlorobenzene （HCB）, a persistent organic pollutant （POP）, has been found in paddy soils. To improve the understanding of HCB contamination in paddy soils, a laboratory simulative study was carried out to inve...Hexachlorobenzene （HCB）, a persistent organic pollutant （POP）, has been found in paddy soils. To improve the understanding of HCB contamination in paddy soils, a laboratory simulative study was carried out to investigate the behavior of HCB in a paddy soil and rice plants. This study was divided into three experiments. First, an experiment aimed to examine the evaporation of HCB in paddy soil. In the second experiment, rice was planted in 10 mg/kg HCB contaminated soil and after pot culture at 3, 6, 9, and 27 weeks （at maturity）, both soil and plant samplings were scheduled to be sampled. The soil samples comprised rhizosphere soil, nortrhizosphere soil, and unplanted contaminated soil, whereas plant samples included shoots, roots, and rice grains （dehusked）. Lastly, in this part, HCB in xylem saps was designed to be examined. The results showed that （1） the HCB translocation from paddy soil to rice by vaporization; （2） the HCB concentration in rice grains was surprisingly high; （3） the observed HCB decrease in rice rhizosphere offers a potential means for in situ HCB degradation; （4） HCB might not be transported along transpiration in rice.展开更多
Hexachlorobenzene （HCB） is a chlorinated aromatic hydrocarbon that was widely used for seed dressing in prevention of fungal growth on crops, and also as a component of fireworks, ammunition, and synthetic rubbers. ...Hexachlorobenzene （HCB） is a chlorinated aromatic hydrocarbon that was widely used for seed dressing in prevention of fungal growth on crops, and also as a component of fireworks, ammunition, and synthetic rubbers. Because of its resistance to degradation and mobility, HCB is widely distributed throughout the environment and is accumulated through food chains in different ecosystems. In this study, a preliminary investigation was carried out on the bioaccumulation and the toxic effects of HCB in the microbial （protozoan in particular） communities in the Fuhe River, Wuhan, a water body receiving industrial wastewaters containing HCB and other pollutants, using the standardized polyurethane foam units （PFU） method. Field samples were taken from eight stations established along the Fuhe River in January and August 2006. The concentration ratios of HCB in microbial communities and in water were 9.66-18.64, and the microbial communities accumulated 13.29-56.88 μg/L of HCB in January and 0.82-10.25 μg/L HCB in August. Correlation analysis showed a negative correlation between the HCB contents in the microbial assemblage, and the number of species and the diversity index of the protozoan communities. This study demonstrated the applicability of the PFU method in monitoring the effects of HCB on the level of microbial communities.展开更多
Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe R...Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of γ 666, p,p' DDT and HCB followed pseudo first order kinetics in different sediments. But, the extents and rates of degradation were different, even the other conditions remained the same. Anaerobic degradation rates of γ 666, p,p' DDT and HCB were 0 020 d -1 , 0 009 d -1 and 0 035 month -1 respectively for the sediments without additional carbon resources. However, with addition of carbon resources, the anaerobic degradation rates of γ 666, p, p ' DDT and HCB were 0 071 d -1 , 0 054 d -1 and 0 088 month -1 in the original sediments respectively. After removing NOM, the rates were decreased to 0 047 d -1 , 0 037 d -1 and 0 066 month -1 ; in the sediments removed NOM and HMO, the rates were increased to 0 067 d -1 , 0 059 d -1 and 0 086 month -1 . These results indicated that NOM in the sediments accelerated the anaerobic degradation of γ 666, p,p' DDT and HCB; the HMO inhibited the anaerobic degradation of γ 666, p,p' DDT and HCB.展开更多
The impacts of contact time on the extractability, the availability of bexachlorobenzene （HCB） in different soils （paddy soil, red soil, and fluvo-aquic soil） and bioaccumulation in earthworm Eisenia foetida were ...The impacts of contact time on the extractability, the availability of bexachlorobenzene （HCB） in different soils （paddy soil, red soil, and fluvo-aquic soil） and bioaccumulation in earthworm Eisenia foetida were investigated under controlled conditions in laboratory. Results indicated that the aging rate of HCB displaying a biphasic character in different soils： a rapid aging in the first 60 d followed by a slow aging in the next 120 d incubation time. Moreover, most of extractable HCB （about 90%） decline occurred in the first 60 d after HCB was spiked into the soils. The aging rate of HCB in the paddy soil was higher than that in the fluvo-aquic soil or the red soil. The amount of HCB accumulated in the earthworms and its accumulative ability, expressed as a bioaccumulation factor （BAF）, declined as the aging time increased from 1 to 180 d. Although the extractable HCB decreased with increasing residence time in soil, much of HCB could still be accumulated by earthworms （457.6-984.3 ng/g） through bioaccumulation, which poses a potential risk to soil ecological safety.展开更多
During the period 1955-1959, approximately 4000 people in southeast Anatolia developed porphyria due to the ingestion of hexachlorobenzene (HCB), a fungicide added to wheat seedlings. These HCB exposures subsequently ...During the period 1955-1959, approximately 4000 people in southeast Anatolia developed porphyria due to the ingestion of hexachlorobenzene (HCB), a fungicide added to wheat seedlings. These HCB exposures subsequently led to the development of bullae on sun-exposed areas, hyperpigmentation, hypertrichosis, and porphyrinuria. The condition was called kara yara or 'black sore.' Many of the breast-fed children under the age of 2 years whose mothers had ingested HCB-treated grain died from a disease known as pembe yara or 'pink sore.' In this follow-up study of 252 patients, 20-30 years postexposure, there were 162 males and 90 females, with an average current age of 35.7 years, an average of onset of 7.6 years, and a duration of 2.2 years. Many patients had dermatologic, neurologic, and orthopedic symptoms and signs. The observed clinical findings include scarring of the face and hands (83.7％), hyperpigmentation (65％), hypertrichosis (44.8％), pinched facies (40.1％), painless arthritis (70.2％), small hands (66.6％), sensory shading (60.6％), myotonia (37.9％), cogwheeling (41.9％), enlarged thyroid (34.9％), and enlarged liver (4.8％). Urine and stool porphyrin levels were determined in all patients, and 17 have at least one of the porphyrins elevated. A total of 56 specimens of human milk obtained from mothers with porphyria were analyzed for HCB. The average value was 0.51 ppm in HCB-exposed patients compared to 0.07 ppm in unexposed controls. Offspring of mothers with three decades of HCB-induced porphyria appear normal. 1989 Academic Press, Inc.展开更多
文摘The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB- and HBC- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several new low-lying electroinc states are found, and the linear triplet structures are found to have the lowest energy. For the anions, the 2 ∑+ states are lower in energy than the 2Π states. For HCB, the 3Π state is 15.38kcal·mol-1 more stable than the 3∑- state, and for HBC the 3Π is 2.51kcal·mol-1 below the 3∑- state at the first order configuration interaction (FOCI) level. The barriers of the conversion of HBC(3Π) to HCB(3Π), HBC(1△(1A1)) to HCB(1A’C3) and HBC(1△(1A2)) to HCB(1A"C3) are 23.21, 12.97 and 21.09kcal·mol-1,respectively. The activation energies of the conversion of HBC-(2∑+) to HCB(2∑+) and HCB-(2Π) to HBC-(2Π) are 18.13 and 25.88kcal·mol-1, respectively. A symmetry breaking phenomenon is observed in several states. The harmonic vibrational frequencies of the neutral molecules and the anions are also reported to provide information for the possible experimental observation of these species.
基金supported by the Knowledge Innova-tion Program of the Chinese Academy of Sciences(No.KZCX2-YW-420)the National Natural Science Foun-dation of China(No.20621703).
文摘Decomposition of hexachlorobenzene(HCB)was investigated over several metal oxides(i.e.,MgO,CaO,BaO,La2O3,CeO2,MnO2, Fe2O3,and Co3O4)supported on Al2O3,which was achieved in closed system at a temperature of 300°C.Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents.The decomposition effciency of different catalysts for this reaction depends on the nature of the metal oxide used,and Al2O3 supported La2O3 was found to be the most active one.Pe...
文摘Hexachlorobenzene （HCB）, a persistent organic pollutant （POP）, has been found in paddy soils. To improve the understanding of HCB contamination in paddy soils, a laboratory simulative study was carried out to investigate the behavior of HCB in a paddy soil and rice plants. This study was divided into three experiments. First, an experiment aimed to examine the evaporation of HCB in paddy soil. In the second experiment, rice was planted in 10 mg/kg HCB contaminated soil and after pot culture at 3, 6, 9, and 27 weeks （at maturity）, both soil and plant samplings were scheduled to be sampled. The soil samples comprised rhizosphere soil, nortrhizosphere soil, and unplanted contaminated soil, whereas plant samples included shoots, roots, and rice grains （dehusked）. Lastly, in this part, HCB in xylem saps was designed to be examined. The results showed that （1） the HCB translocation from paddy soil to rice by vaporization; （2） the HCB concentration in rice grains was surprisingly high; （3） the observed HCB decrease in rice rhizosphere offers a potential means for in situ HCB degradation; （4） HCB might not be transported along transpiration in rice.
基金Project supported by the Key Project of Chinese Ministry of Education(No.104250).
文摘Hexachlorobenzene （HCB） is a chlorinated aromatic hydrocarbon that was widely used for seed dressing in prevention of fungal growth on crops, and also as a component of fireworks, ammunition, and synthetic rubbers. Because of its resistance to degradation and mobility, HCB is widely distributed throughout the environment and is accumulated through food chains in different ecosystems. In this study, a preliminary investigation was carried out on the bioaccumulation and the toxic effects of HCB in the microbial （protozoan in particular） communities in the Fuhe River, Wuhan, a water body receiving industrial wastewaters containing HCB and other pollutants, using the standardized polyurethane foam units （PFU） method. Field samples were taken from eight stations established along the Fuhe River in January and August 2006. The concentration ratios of HCB in microbial communities and in water were 9.66-18.64, and the microbial communities accumulated 13.29-56.88 μg/L of HCB in January and 0.82-10.25 μg/L HCB in August. Correlation analysis showed a negative correlation between the HCB contents in the microbial assemblage, and the number of species and the diversity index of the protozoan communities. This study demonstrated the applicability of the PFU method in monitoring the effects of HCB on the level of microbial communities.
文摘Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of γ 666, p,p' DDT and HCB followed pseudo first order kinetics in different sediments. But, the extents and rates of degradation were different, even the other conditions remained the same. Anaerobic degradation rates of γ 666, p,p' DDT and HCB were 0 020 d -1 , 0 009 d -1 and 0 035 month -1 respectively for the sediments without additional carbon resources. However, with addition of carbon resources, the anaerobic degradation rates of γ 666, p, p ' DDT and HCB were 0 071 d -1 , 0 054 d -1 and 0 088 month -1 in the original sediments respectively. After removing NOM, the rates were decreased to 0 047 d -1 , 0 037 d -1 and 0 066 month -1 ; in the sediments removed NOM and HMO, the rates were increased to 0 067 d -1 , 0 059 d -1 and 0 086 month -1 . These results indicated that NOM in the sediments accelerated the anaerobic degradation of γ 666, p,p' DDT and HCB; the HMO inhibited the anaerobic degradation of γ 666, p,p' DDT and HCB.
基金supported by the Open Fund of State Key Laboratory of Soil and Sustainable Agriculture, In- stitute of Soil Science, Chinese Academy of Sciences (No. 0812000037)the Natural Science Research Program of Anhui Education Department of China (No. 2006KJ175B)
文摘The impacts of contact time on the extractability, the availability of bexachlorobenzene （HCB） in different soils （paddy soil, red soil, and fluvo-aquic soil） and bioaccumulation in earthworm Eisenia foetida were investigated under controlled conditions in laboratory. Results indicated that the aging rate of HCB displaying a biphasic character in different soils： a rapid aging in the first 60 d followed by a slow aging in the next 120 d incubation time. Moreover, most of extractable HCB （about 90%） decline occurred in the first 60 d after HCB was spiked into the soils. The aging rate of HCB in the paddy soil was higher than that in the fluvo-aquic soil or the red soil. The amount of HCB accumulated in the earthworms and its accumulative ability, expressed as a bioaccumulation factor （BAF）, declined as the aging time increased from 1 to 180 d. Although the extractable HCB decreased with increasing residence time in soil, much of HCB could still be accumulated by earthworms （457.6-984.3 ng/g） through bioaccumulation, which poses a potential risk to soil ecological safety.
文摘During the period 1955-1959, approximately 4000 people in southeast Anatolia developed porphyria due to the ingestion of hexachlorobenzene (HCB), a fungicide added to wheat seedlings. These HCB exposures subsequently led to the development of bullae on sun-exposed areas, hyperpigmentation, hypertrichosis, and porphyrinuria. The condition was called kara yara or 'black sore.' Many of the breast-fed children under the age of 2 years whose mothers had ingested HCB-treated grain died from a disease known as pembe yara or 'pink sore.' In this follow-up study of 252 patients, 20-30 years postexposure, there were 162 males and 90 females, with an average current age of 35.7 years, an average of onset of 7.6 years, and a duration of 2.2 years. Many patients had dermatologic, neurologic, and orthopedic symptoms and signs. The observed clinical findings include scarring of the face and hands (83.7％), hyperpigmentation (65％), hypertrichosis (44.8％), pinched facies (40.1％), painless arthritis (70.2％), small hands (66.6％), sensory shading (60.6％), myotonia (37.9％), cogwheeling (41.9％), enlarged thyroid (34.9％), and enlarged liver (4.8％). Urine and stool porphyrin levels were determined in all patients, and 17 have at least one of the porphyrins elevated. A total of 56 specimens of human milk obtained from mothers with porphyria were analyzed for HCB. The average value was 0.51 ppm in HCB-exposed patients compared to 0.07 ppm in unexposed controls. Offspring of mothers with three decades of HCB-induced porphyria appear normal. 1989 Academic Press, Inc.
