Humic acid is rich in highly electronegative oxygen-containing organic functional groups,so it has high reactivity and can adsorb phthalic acid ester(PAEs)in the environment to reduce the risk of environmental polluti...Humic acid is rich in highly electronegative oxygen-containing organic functional groups,so it has high reactivity and can adsorb phthalic acid ester(PAEs)in the environment to reduce the risk of environmental pollution from PAEs.In this paper,the extraction,characterization and adsorption models of humic acid were reviewed,and the research status of adsorption of PAEs by humic acid was further summarized.Based on these,the feasibility and observable application prospect of humic acid as a cheap adsorbent were analyzed.展开更多
Abiotic degradability of four phthalic acid esters (PAEs) in the aquatic phase was evaluated over a wide pH range 5-9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunli...Abiotic degradability of four phthalic acid esters (PAEs) in the aquatic phase was evaluated over a wide pH range 5-9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunlight irradiation for evaluating the degradation rate via hydrolysis or photolysis plus hydrolysis, respectively, at ambient temperature for 140 d from autumn to winter in Osaka, Japan. The efficiency of abiotic degradation of the PAEs with relatively short alkyl chains, such as butylbenzyl phthalate (BBP) and di-nbutyl phthalate (DBP), at neutral pH was significantly lower than that in the acidic or alkaline condition. Photolysis was considered to contribute mainly to the total abiotic degradation at all pH. Neither hydrolysis nor photolysis of di-ethylhexyl phthalate (DEHP) proceeded significantly at any pH, especially hydrolysis at neutral pH was negligible. On the other hand, the degradation rate of di- isononyl phthalate (DINP) catalyzed mainly by photolysis was much higher than those of the other PAEs, and was almost completely removed during the experimental period at pH 5 and 9. As a whole, according to the half-life (t1/2) obtained in the experiments, the abiotic degradability of the PAEs was in the sequence: DINP (32-140 d) 〉 DBP (50-360 d), BBP (58-480 d) 〉 DEHP (390-1600 d) under sunlight irradiation (via photolysis plus hydrolysis). Although the abiotic degradation rates for BBP, DBP, and DEHP are much lower than the biodegradation rates reported, the photolysis rate for DINP is comparable to its biodegradation rate in the acidic or alkaline condition.展开更多
Biodegradability of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBP), di-ethylhexyl phthalate (DEHP), and di-isononyl phthalate (DINP) under an anaerobic condition was evaluated using three natural sedi...Biodegradability of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBP), di-ethylhexyl phthalate (DEHP), and di-isononyl phthalate (DINP) under an anaerobic condition was evaluated using three natural sediment microcosms obtained from ponds in Osaka, which had not been significantly polluted by the chemicals. The degradabilities of the four phthalic acid esters(PAEs) were analyzed by a first-order kinetic model with a lag phase and ranked as DBP〉BBP〉〉DEHP〉DINP. The PAEs with shorter alkyl-chains, DBP and BBP, were degraded with quite short lag phases near to zero and short half-lives of a few days. The PAEs with longer alkyl-chains, DEHP and DINP, were degraded with lag phases of 5-30 d and the quite long half-lives of a couple of hundred days. Although no data was available on the anaerobic biodegradability of D1NP before this study, it was clarified that DINP can be degraded with slow degradation rates. The fact that all the three intact sediments were capable of biodegradation of the PAEs suggests that potential of anaerobic biodegradation of PAEs is widespread in the aquatic environment.展开更多
Based on quantitative structure-property relationship (QSPR) of organic compounds, the molecular connectivity indices of 21 phthalic acid ester compounds were extracted. Relationship between the physicochemical prop...Based on quantitative structure-property relationship (QSPR) of organic compounds, the molecular connectivity indices of 21 phthalic acid ester compounds were extracted. Relationship between the physicochemical properties (n-octanol/air partition coefficient, vapor pressure, water solubility) and the molecular connectivity indices of phthalic acid ester compounds have been established by multiple linear regression (MLR) method. The results showed that the zero-order valence connectivity index (0Xu) is the topology parameter which affects octanol/water partition coefficient and water solubility, and the topology parameter which affects vapor pressure is the first-order connectivity index (1X). This indicated to a certain extent_that the molecular connectivity indices can be well used to express the quantitative relationship between the physicochemical properties and structure descriptions of phthalic acid ester compounds. The models constructed have good robustness and highly predictive capability.展开更多
The pollution from polycyclic aromatic hydrocarbons(PAHs) and phthalic acid esters(PAEs) in the surface water of the rapidly urbanized Yangtze River Delta region was investigated.Fourteen surface water samples wer...The pollution from polycyclic aromatic hydrocarbons(PAHs) and phthalic acid esters(PAEs) in the surface water of the rapidly urbanized Yangtze River Delta region was investigated.Fourteen surface water samples were collected in June 2010.Water samples were liquid-liquid extracted using methylene chloride and analyzed by gas chromatography-mass spectrometry.Concentrations of PAHs and PAEs ranged 12.9-638.1 ng/L and 61-28550 ng/L,respectively.Fluoranthene,naphthalene,pyrene,phenanthrene,di-2ethylhexyl phthalate,and di-n-butyl phthalate were the most abundant compounds in the samples.The water samples were moderately polluted with benzo[a]pyrene according to China's environmental quality standard for surface water.The two highest concentrations of PAHs and PAEs occurred in samples from Taihu Lake,Wuxi City and the western section of Yangchenghu Lake.Potential sources of pollution at S7 were petroleum combustion and the plastics industry,and at Yangchenghu Lake were petroleum combustion and domestic waste.Pollution in samples from the Beijing-Hangzhou Grand Canal originated from diesel engines.There were no obvious sources of pollution for the other water samples.These results can be used as reference levels for future monitoring programs of pollution from PAHs and PAEs.展开更多
After the impoundment of the Three Gorges Reservoir(TGR), the hydrological situation of the reservoir has changed greatly. The concentration and distribution of typical persistent organic pollutants in water and sed...After the impoundment of the Three Gorges Reservoir(TGR), the hydrological situation of the reservoir has changed greatly. The concentration and distribution of typical persistent organic pollutants in water and sediment have also changed accordingly. In this study, the concentration, distribution and potential sources of 16 polycyclic aromatic hydrocarbons(PAHs) and 6 phthalic acid esters(PAEs) during the water drawdown and impoundment periods were investigated in water and sediment from the TGR. According to our results, PAHs and PAEs showed temporal and spatial variations. The mean ΣPAH and ΣPAE concentrations in water and sediment were both higher during the water impoundment period than during the water drawdown period. The water samples from the main stream showed larger ΣPAH concentration fluctuations than those from tributaries. Both the PAH and PAE concentrations meet the Chinese national water environmental quality standard(GB 3838-2002). PAH monomers with 2–3 rings and 4 rings were dominant in water, and 4-ring and 5–6-ring PAHs were dominant in sediment. Di-n-butyl phthalate(DBP) and di-2-ethylhexyl phthalate(DEHP)were the dominant PAE pollutants in the TGR. DBP and DEHP had the highest concentrations in water and sediment, respectively. The main source of PAHs in water from the TGR was petroleum and emissions from coal and biomass combustion, whereas the main sources of PAHs in sediments included coal and biomass combustion, petroleum, and petroleum combustion. The main source of PAEs in water was domestic waste, and the plastics and heavy chemical industries were the main sources of PAEs in sediment.展开更多
The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with 14C-labelin...The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with 14C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Ele- mental analysis and Fourier Transform Infrared Spectro- photometer (FTIR) suggested that high KA value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The KA values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that non- specific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.展开更多
A novel series of para-diiodobenzene derivatives, 3,6-diiodo-4,5-dialkyl-phthalic acid dimethyl esters, were prepared via cycloaddition of two TMS-substituted alkynes and dimethyl acetylenedicarboxylate, which was med...A novel series of para-diiodobenzene derivatives, 3,6-diiodo-4,5-dialkyl-phthalic acid dimethyl esters, were prepared via cycloaddition of two TMS-substituted alkynes and dimethyl acetylenedicarboxylate, which was mediated by zirconocene. After iodination, three new compounds of 3,6-diiodo-4,5-dimethyl(dipropyl, dibutyl)-phthalic acid dimethyl esters (3a, 3b, 3c) were synthesized in high region-selectivity and yields, and characterized by NMR. The crystal structures were determined by single-crystal X-ray diffraction. The crystal of 3a (C12H121204, Mr = 474.02) belongs to the triclinic system, space group Pi with a = 7.6238(10), b = 9.4571(12), c = 10.8221(14) A, a = 66.611(10), fl = 88.511(12), 7 : 77.604(11)% V= 697.93(16) A3, Z= 2, F(000) = 444, Dc = 2.256 mg/m3, g = 4.509 mm-1, T=133(2) K, S = 1.014, R = 0.0229 and wR = 0.0547 for 2644 observed reflections with I 〉 20(/); the crystal of 3b (C16H201204, Mr - 530.12) is of triclinic system, space group Pi with a = 9.4122(19), b = 10.626(2), c = 11.353(2) A, a = 97.90(3), fl = 113.83(3), y = 110.22(3)°, V= 922.6(3) A3, Z- 2, F(000) = 508, Dc - 1.908 mg/m3, g = 3.422 mm-1, T = 113(2) K, S = 1.115, R = 0.0428 and wR = 0.1072 for 3971 observed reflections with I〉 20(/); the crystal of 3c (ClsH241204, Mr = 558.17) belongs to the monoclinic system, space group P21/c with a = 26.396(2), b = 8.7560(8), c = 25.7970(18) A, fl = 91.721(4)o, V= 5959.6(8) A3, Z = 12, F(000) = 3240, Dc = 1.866 mg/m3,/z = 3.184 mm-l, T= 113(2) K, S = 1.154, R = 0.0424 and wR = 0.0766 for 13056 observed reflections with I 〉 20(/).展开更多
A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes ...A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes in soil samples with n-hexane–acetone(V:V=1:1) as extraction solvent. This method has several advantages, including high extraction efficiency, short time, convenience and simplicity. It can be used to detect polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil.展开更多
文摘Humic acid is rich in highly electronegative oxygen-containing organic functional groups,so it has high reactivity and can adsorb phthalic acid ester(PAEs)in the environment to reduce the risk of environmental pollution from PAEs.In this paper,the extraction,characterization and adsorption models of humic acid were reviewed,and the research status of adsorption of PAEs by humic acid was further summarized.Based on these,the feasibility and observable application prospect of humic acid as a cheap adsorbent were analyzed.
文摘Abiotic degradability of four phthalic acid esters (PAEs) in the aquatic phase was evaluated over a wide pH range 5-9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunlight irradiation for evaluating the degradation rate via hydrolysis or photolysis plus hydrolysis, respectively, at ambient temperature for 140 d from autumn to winter in Osaka, Japan. The efficiency of abiotic degradation of the PAEs with relatively short alkyl chains, such as butylbenzyl phthalate (BBP) and di-nbutyl phthalate (DBP), at neutral pH was significantly lower than that in the acidic or alkaline condition. Photolysis was considered to contribute mainly to the total abiotic degradation at all pH. Neither hydrolysis nor photolysis of di-ethylhexyl phthalate (DEHP) proceeded significantly at any pH, especially hydrolysis at neutral pH was negligible. On the other hand, the degradation rate of di- isononyl phthalate (DINP) catalyzed mainly by photolysis was much higher than those of the other PAEs, and was almost completely removed during the experimental period at pH 5 and 9. As a whole, according to the half-life (t1/2) obtained in the experiments, the abiotic degradability of the PAEs was in the sequence: DINP (32-140 d) 〉 DBP (50-360 d), BBP (58-480 d) 〉 DEHP (390-1600 d) under sunlight irradiation (via photolysis plus hydrolysis). Although the abiotic degradation rates for BBP, DBP, and DEHP are much lower than the biodegradation rates reported, the photolysis rate for DINP is comparable to its biodegradation rate in the acidic or alkaline condition.
文摘Biodegradability of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBP), di-ethylhexyl phthalate (DEHP), and di-isononyl phthalate (DINP) under an anaerobic condition was evaluated using three natural sediment microcosms obtained from ponds in Osaka, which had not been significantly polluted by the chemicals. The degradabilities of the four phthalic acid esters(PAEs) were analyzed by a first-order kinetic model with a lag phase and ranked as DBP〉BBP〉〉DEHP〉DINP. The PAEs with shorter alkyl-chains, DBP and BBP, were degraded with quite short lag phases near to zero and short half-lives of a few days. The PAEs with longer alkyl-chains, DEHP and DINP, were degraded with lag phases of 5-30 d and the quite long half-lives of a couple of hundred days. Although no data was available on the anaerobic biodegradability of D1NP before this study, it was clarified that DINP can be degraded with slow degradation rates. The fact that all the three intact sediments were capable of biodegradation of the PAEs suggests that potential of anaerobic biodegradation of PAEs is widespread in the aquatic environment.
基金Supported by the Natural Science Foundation of Zhejiang Province(LY12B07013,LY12C03009)Public Technology Research Project(Analysis and Measurement)of Zhejiang Province(2013C37098)Science and Technology Project of Zhejiang Province(2009C33163)
文摘Based on quantitative structure-property relationship (QSPR) of organic compounds, the molecular connectivity indices of 21 phthalic acid ester compounds were extracted. Relationship between the physicochemical properties (n-octanol/air partition coefficient, vapor pressure, water solubility) and the molecular connectivity indices of phthalic acid ester compounds have been established by multiple linear regression (MLR) method. The results showed that the zero-order valence connectivity index (0Xu) is the topology parameter which affects octanol/water partition coefficient and water solubility, and the topology parameter which affects vapor pressure is the first-order connectivity index (1X). This indicated to a certain extent_that the molecular connectivity indices can be well used to express the quantitative relationship between the physicochemical properties and structure descriptions of phthalic acid ester compounds. The models constructed have good robustness and highly predictive capability.
基金supported by the National Basic Research Program of China (No. 2009CB421602)the Water Pollution Control and Treatment Special Project (No.2009ZX07527-001)+1 种基金the State Key Laboratory of Environmental Chemistry and Ecotoxicology (No. KF2010-20)the Special Fund for Public Welfare Industry on Environmental Protection (No. 2009467109)
文摘The pollution from polycyclic aromatic hydrocarbons(PAHs) and phthalic acid esters(PAEs) in the surface water of the rapidly urbanized Yangtze River Delta region was investigated.Fourteen surface water samples were collected in June 2010.Water samples were liquid-liquid extracted using methylene chloride and analyzed by gas chromatography-mass spectrometry.Concentrations of PAHs and PAEs ranged 12.9-638.1 ng/L and 61-28550 ng/L,respectively.Fluoranthene,naphthalene,pyrene,phenanthrene,di-2ethylhexyl phthalate,and di-n-butyl phthalate were the most abundant compounds in the samples.The water samples were moderately polluted with benzo[a]pyrene according to China's environmental quality standard for surface water.The two highest concentrations of PAHs and PAEs occurred in samples from Taihu Lake,Wuxi City and the western section of Yangchenghu Lake.Potential sources of pollution at S7 were petroleum combustion and the plastics industry,and at Yangchenghu Lake were petroleum combustion and domestic waste.Pollution in samples from the Beijing-Hangzhou Grand Canal originated from diesel engines.There were no obvious sources of pollution for the other water samples.These results can be used as reference levels for future monitoring programs of pollution from PAHs and PAEs.
基金supported by the Public Interest Scientific Research Fund of the Ministry of Water Resource of China(No.201501042)the National Natural Science Foundation of China(Nos.51309019,51379016)+3 种基金the Young Elite Scientist Sponsorship Program by CAST(No.2015QNRC001)the State-level Public Welfare Scientific Research Institutes Basic Scientific Research Business Project of China(No.CKSF2017062/SH)the Technology Demonstration Project of the Ministry of Water Resources of China(No.SF-201602)supported by the Brook Byers Institute for Sustainable Systems,Georgia Institute of Technology(Georgia Tech Hightower No.1365802)
文摘After the impoundment of the Three Gorges Reservoir(TGR), the hydrological situation of the reservoir has changed greatly. The concentration and distribution of typical persistent organic pollutants in water and sediment have also changed accordingly. In this study, the concentration, distribution and potential sources of 16 polycyclic aromatic hydrocarbons(PAHs) and 6 phthalic acid esters(PAEs) during the water drawdown and impoundment periods were investigated in water and sediment from the TGR. According to our results, PAHs and PAEs showed temporal and spatial variations. The mean ΣPAH and ΣPAE concentrations in water and sediment were both higher during the water impoundment period than during the water drawdown period. The water samples from the main stream showed larger ΣPAH concentration fluctuations than those from tributaries. Both the PAH and PAE concentrations meet the Chinese national water environmental quality standard(GB 3838-2002). PAH monomers with 2–3 rings and 4 rings were dominant in water, and 4-ring and 5–6-ring PAHs were dominant in sediment. Di-n-butyl phthalate(DBP) and di-2-ethylhexyl phthalate(DEHP)were the dominant PAE pollutants in the TGR. DBP and DEHP had the highest concentrations in water and sediment, respectively. The main source of PAHs in water from the TGR was petroleum and emissions from coal and biomass combustion, whereas the main sources of PAHs in sediments included coal and biomass combustion, petroleum, and petroleum combustion. The main source of PAEs in water was domestic waste, and the plastics and heavy chemical industries were the main sources of PAEs in sediment.
文摘The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with 14C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Ele- mental analysis and Fourier Transform Infrared Spectro- photometer (FTIR) suggested that high KA value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The KA values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that non- specific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.
文摘A novel series of para-diiodobenzene derivatives, 3,6-diiodo-4,5-dialkyl-phthalic acid dimethyl esters, were prepared via cycloaddition of two TMS-substituted alkynes and dimethyl acetylenedicarboxylate, which was mediated by zirconocene. After iodination, three new compounds of 3,6-diiodo-4,5-dimethyl(dipropyl, dibutyl)-phthalic acid dimethyl esters (3a, 3b, 3c) were synthesized in high region-selectivity and yields, and characterized by NMR. The crystal structures were determined by single-crystal X-ray diffraction. The crystal of 3a (C12H121204, Mr = 474.02) belongs to the triclinic system, space group Pi with a = 7.6238(10), b = 9.4571(12), c = 10.8221(14) A, a = 66.611(10), fl = 88.511(12), 7 : 77.604(11)% V= 697.93(16) A3, Z= 2, F(000) = 444, Dc = 2.256 mg/m3, g = 4.509 mm-1, T=133(2) K, S = 1.014, R = 0.0229 and wR = 0.0547 for 2644 observed reflections with I 〉 20(/); the crystal of 3b (C16H201204, Mr - 530.12) is of triclinic system, space group Pi with a = 9.4122(19), b = 10.626(2), c = 11.353(2) A, a = 97.90(3), fl = 113.83(3), y = 110.22(3)°, V= 922.6(3) A3, Z- 2, F(000) = 508, Dc - 1.908 mg/m3, g = 3.422 mm-1, T = 113(2) K, S = 1.115, R = 0.0428 and wR = 0.1072 for 3971 observed reflections with I〉 20(/); the crystal of 3c (ClsH241204, Mr = 558.17) belongs to the monoclinic system, space group P21/c with a = 26.396(2), b = 8.7560(8), c = 25.7970(18) A, fl = 91.721(4)o, V= 5959.6(8) A3, Z = 12, F(000) = 3240, Dc = 1.866 mg/m3,/z = 3.184 mm-l, T= 113(2) K, S = 1.154, R = 0.0424 and wR = 0.0766 for 13056 observed reflections with I 〉 20(/).
基金support from the Fundamental Research Funds for the Institute of Hydrogeology and Environmental Geology, the Chinese Academy of Geological Sciences (SK201204)
文摘A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes in soil samples with n-hexane–acetone(V:V=1:1) as extraction solvent. This method has several advantages, including high extraction efficiency, short time, convenience and simplicity. It can be used to detect polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil.