太阳光下水中2,4,6-三氯酚的光解机制研究

对比研究了太阳光下2,4,6-三氯酚（2,4,6-TCP）在纯水,可溶性有机质（DOM）溶液和实际地表水中的光解情况.结果表明,2,4,6-TCP在纯水中主要为直接光解和自敏化光解,涉及的活性物种为单线态氧;在DOM水溶液中主要为直接光解和敏化光解,涉及的活性物种为单线态氧和羟基自由基;2,4,6-TCP在纯水,DOM溶液和实际地表水中的光解速率均随溶液含氧量的提高而增加.太阳光可见区对2,4,6-TCP直接光解没有贡献,UVA贡献为72.60%,而当有DOM存在时,可见光区对2,4,6-TCP的光解贡献为12.39%,UVA的贡献为52.73%.2,4,6-TCP在实际地表水中的光解与在DOM水溶液中的光解类似,都表现为通氮抑制光解,通氧促进光解,并且光谱贡献率也十分接近,表明溶解氧和DOM是2,4,6-TCP在地表水中间接光解的主要影响因素.     

Combined treatment of phenolic wastewater by wet air oxidation and activated sludge

Wet air oxidation (WAO) is employed in this work for treating high concentration chemical wastewater containing phenol and/or phenolic compounds. Experimental results indicate that over 90% removal of phenol or phenolic compounds can be efficiently achieved in the WAO process. Despite of the high treatment efficiency of the WAO process, the treated wastewater, however, still retains relatively high chemical oxygen demand (COD) concentration and does not meet the safe discharge standard. Hence further treatment of the WAO treated wastewater by an aerobic biological treatment using acclimatized activated sludge is necessary. It is found in the present studies that the combined process, if appropriately operated, is capable of drastically reducing the COD concentration of the high concentration chemical wastewater to meet the safe discharge requirement. The operating conditions of the combined process are investigated to determine their respective effects on the overall treatment efficiency. The experimental data also indicate that the oxidation reaction can be represented by a first order kinetics in terms of the component or COD concentration. For both single component and multicomponent wastewaters, the WAO process was found to have different activation energy for oxidation below and above 200°C, suggesting possibly different reaction mechanisms between these temperature ranges. The experimental results provided in the present work can provide significant and practical information for optimizing the combined treatment method.     

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Abstract

Three collectives of substances - plastics, plant nutrients, biotoxins - are candidates for monitoring programmes that could keep track of the quality of ocean waters for vital life processes. All three are not subject to systematic surveillance at present. They are each characterized by long residence times in the marine environment, by increasing influx, and by growing evidence of their deleterious impacts on living systems.     

环戊烯臭氧化反应瞬变物种产生机制

大气中烯烃臭氧化反应产物是二次有机气溶胶(SOA)形成的重要前体物. 运用自行组建的低温基质隔离系统研究环戊烯臭氧化反应的瞬变物种产生机制. 采用程序升温方法,将温度从6 K升至115 K,用傅里叶红外光谱仪检测不同温度下生成的活性中间体,并将试验值与理论计算值、文献报道值进行对比,以确定中间体构型. 结果表明:环戊烯臭氧化反应生成的中间体——POZ(初级臭氧化物)、SOZ(二次臭氧化物)和CI(一分子羰基氧化物和一分子醛或酮)被成功检测到. 其中,POZ的特征吸收峰在705和946 cm-1处,对应O—O—O反对称伸缩振动和环变形振动;SOZ特征吸收峰在939 cm-1处,对应C—O伸缩振动;CI的特征吸收峰在1 733和853 cm-1处,分别对应CO伸缩振动和O—O伸缩振动. 据此,环戊烯臭氧化反应遵循Criegee机制. 采用4种量子化学计算方法——B3LYP/6-311++G(d,2p)、B3LYP/6-311++G(3df,3pd)、MP2/aug-cc-pvdz和PW91PW91/6-311++G(3df,3pd),计算POZ、SOZ和CI特征吸收峰的振动频率,其中POZ在705 cm-1处吸收峰的振动频率计算值分别为725、698、703、680 cm-1;SOZ在1 030 cm-1处吸收峰的振动频率计算值分别为1 017、1 018、1 025和993 cm-1;CI在1 733 cm-1处吸收峰的振动频率计算值分别为1 796、1 803、1 732和1 745 cm-1.表明MP2/aug-cc-pvdz计算的特征振动频率与试验值最接近.      

鲍鱼对2种多环芳烃的富集动力学研究

为探究多环芳烃(PAHs)在海洋生物体内富集过程,选择皱纹盘鲍(Haliotis discus hannai)作为受试生物,应用半静态双箱动力学模型,分别考察了3-甲基菲和9,10-甲基蒽2种多环芳烃在皱纹盘鲍体内的富集动力学过程,通过非线性拟合获得鲍鱼对2种多环芳烃的吸收速率常数(K_1)、释放速率常数(K_2)、生物富集因子(BCF),以及平衡状态下鲍鱼体内2种多环芳烃的含量(Cmax)、生物学半衰期(t_(1/2))等动力学参数。结果表明,鲍鱼对9,10-甲基蒽富集动力学参数K_1、K_2、BCF、Cmax、t_(1/2)的平均值分别为4.9437、0.406、13.59、790.03μg·L~(-1)、3.78 d。鲍鱼对3-甲基菲富集动力学参数K_1、K_2、BCF、Cmax、t_(1/2)的平均值分别为2.3023、0.367、5.97、354.37μg·L~(-1)、3.13 d。鲍鱼在不同浓度下对3-甲基菲和9,10-甲基蒽的生物富集过程均符合双箱动力学模型。     

长期施用粪肥土壤中喹诺酮类抗生素的含量与分布特征

针对珠江三角洲地区长期施用粪肥的“无公害蔬菜”生产基地,利用固相萃取-高效液相色谱-串联质谱(LC-MS/MS)分析方法,探讨了土壤中喹诺酮类(QNs)抗生素4种化合物的含量与分布特征.结果表明,土壤中4种化合物的总含量(ΣQNs)为3.97~32.03μg/kg,平均17.99μg/kg.各化合物的检出率除了洛美沙星(92%)以外均为100%,最高含量为17.21μg/kg,平均含量为0.17~9.31μg/kg,以环丙沙星为主,其次是诺氟沙星和恩诺沙星.化合物的含量与组成特征无论在平面上还是在剖面上均存在明显的空间分布差异,且随着深度增加含量迅速降低,但在80cm深度仍有检出.珠江三角洲地区长期施用粪肥蔬菜基地土壤中喹诺酮类抗生素含量较低,土壤生态毒性风险较小,但各化合物均很高的检出率而导致的协同生态毒性尤其是耐药性问题值得进一步研究.     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Species of Trace Metals,Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Abstract

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^?1, dry weight in fulvic acid and 820μg g^?1 in humic acid) and lead (821μg g^?1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

The Reuse of Urban and Industrial Waste in Tai-Lin-Pu Reclamation Project,Taiwan

Abstract

This study introduces the principles of KMG's (Kaoshiung Municipal Government) dealing with the non-poisonous urban and industrial waste through reclamation of shore land in reinforcing a sense of coastal protection and land development in Tai-Lin-Pu coastal area, southern Taiwan.

Through a series of experimental studies, we found that substitutes of coarse aggregate with a broad spectrum of integrating slag powder, fly ash, and cementitious material can be obtained with a benefit up to 80% saving of cement. the integrated aggregates from the non-poisonous industrial wastes were subsequently made into armour units and used in the field tests at Tai-Lin-Pu coastal area, where the shorelines are seriously eroded. After being subjected to several severe typhoon advents, the results showed that the waste-made units used as the protection breakwater, together with construction wastes and excavated soil as the filling material, prove to be an effective practice in utilizing recycled urban waste to reclaim erosive shore lands. Moreover, this study also demonstrates that through detailed analysis of the waste characteristics, scrap material could be turned into valuable construction aggregates, and highlights the value of non-poisonous urban and industrial waste as a alternative resource for the shore protection engineering.     

Assessment of mutagenic potency of source water treated by ozone and adsorption processes

This research utilized the Ames test to determine the mutagenicity of water treated by advanced processes, including ozonation and granular activated carbon (GAC). Raw water samples for this research included those obtained from the Pan Hsin waterworks as well as samples containing humic acids. Treated samples were collected from the pilot‐scale advanced treatment plant. The Ames test was used to measure the mutagenicity of the water after each treatment process. For the Pan Hsin raw water samples treated with ozone or GAC, it was indicated that, regardless of whether samples were preozonated or not, they all showed a mutagenic potency less than 2 once the S9 enzyme was added. This level of mutagenicity is insignificant. The prepared humic acid samples, on the other hand, demonstrated a significant reduction in mutagenicity after the pre‐ozonation process, indicating that preozonation can lower the degree of mutagenicity. Furthermore, the mutagenicity of the prepared humic acid samples gradually decreased after the advanced treatment process. However, when chlorine was added later to these samples, the mutagenicity increased again. This research shows that the use of O3/GAC processes to treat water can successfully lower mutagenicity, indicating a great potential for applications in the treatment of drinking water.