Fe~(3+)掺杂TiO_2/凹凸棒复合材料的光催化性能

采用酸催化的溶胶-凝胶法制备了一系列Fe3+掺杂TiO2/凹凸棒(Fe3+-TiO2/ATP)复合光催化剂材料。在可见光条件下,以亚甲基蓝(MB)溶液的光催化降解反应,评价了样品的光催化性能,研究了TiO2负载量、Fe3+掺杂量和焙烧温度对复合材料光催化性能的影响。在单因素实验的基础上,采用正交实验设计(L25(53))优化了催化剂的制备条件。光催化实验结果表明,MB在复合材料上的光催化降解反应遵循Langmuir-Hinshelwood(L-H)动力学模型。正交实验结果表明,当TiO2负载量为15%、Fe3+掺杂量为0.5%和焙烧温度为550℃时,得到的复合材料对MB的光催化降解效率最佳,测得表观反应速率常数kapp为6.09×10-3min-1,反应4 h后MB的降解率(Dt)可达75.88%,相同实验条件下与P25(1.51×10-3min-1)相比较,反应速率提高了4.03倍,降解率提高了45.05%。另外,复合材料的沉降性能优于P25,易于分离,是一类有应用前景的复合光催化剂。     

Synthesis of Cl2- to Cl4-diphenylsulfides and Cl1- to Cl3-dibenzothiophenes

The synthesis of eleven environmentally relevant mono-, di- and trichlorodibenzothiophenes (2) by photochemical ring-closure of polychlorodiphenylsulfides (1) is described. All monochlorodibenzothiophenes were additionally synthesized starting with a chlorothiophenol in a three-step reaction adapted from the synthesis of methyldibenzothiophenes.     

Toxicity of mixtures of phosphamidon and methidathion to lobsters (Homarusamericanus)

The joint toxicity of mixtures of phosphamidon and methidathion to adult lobsters ($\text{Homarus}$$\text{americanus}$) is greater than additive in tests with the combined 48-h toxicity unit of the mixtures totalling 0.25, 0.5 and 1.0 units. The largest magnification factor for greater than additive toxicity occurred where phosphamidon and methidathion contributed to the total toxicity unit in a ratio of 1:1.5 and was progressively smaller for ratios of 1:4.4 and 2:1.     

Consultant Guide/1987

ABSTRACT

This study considers the characteristics of ground-level ozone (O₃) in five Korean cities over a time period of 6-8 years. The focus of this study is daily maximum 1-hr and 8-hr concentrations. For all the study cities in the period examined, the mean and most of the percentiles (5, 10, 25, 50, 75, 90, and 95) for the daily maximum 1-hr and 8hr concentrations showed increasing trends, although not all trends were statistically significant. The daily maximum 1-hr and 8-hr concentrations slowly increased during late winter, and peaks were attained during the summer season (from May to September). All the selected cities exhibited a high degree of correlation between their daily maximum 8-hr and 1-hr concentrations. The daily maximum 8-hr concentrations, which were climatologi-cally equivalent to the Korean 1 hr/100 parts per billion (ppb) standard, were higher than the current 8 hr/60 ppb by a difference of 8-16 ppb. Compared with other cities in Korea, Seoul recorded a substantially higher frequency of days and hours with concentrations above 1 hr/100 ppb, and a higher frequency of days with concentrations above 8 hr/60 ppb and 8 hr/80 ppb. Seoul also recorded a substantially higher frequency of hours with concentrations above 1 hr/100 ppb than days with concentrations above 1 hr/100 ppb, implying that on some days severe exceedances persisted for more than one hour per day. During multiple-day episodes a North Pacific High dominated Korea, which is quite typical in Korea during the summer season.     

TS-1分子筛催化O3/H2O2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系(O3/H2O2/TS-1)对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸(初始浓度为100 mg/L)的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

Adsorption/desorption of linear alkylbenzenesulfonate (LAS) and azoproteins by/from activated sludge flocs

Our study investigated the adsorption/desorption by/from activated sludge flocs, dispersed in river water or in diluted wastewater, of organic compounds (C(11)-LAS, azoalbumin and azocasein) at concentrations relevant to environmental conditions. Activated sludge flocs, used as a model of biological aggregates, are characterized by a very heterogeneous matrix able to sorb the three organic compounds tested at 4 degrees C. The adsorbed amount of C(11)-LAS by activated sludge flocs was higher than that of azocasein or azoalbumin, as shown by the Freundlich parameters (K(ads)=8.6+/-1.7, 1.6+/-0.3 and 0.3+/-0.1 micromol(1-1/n)g(-1)l(1/n) for C(11)-LAS, azocasein and azoalbumin, respectively; n=3 sludges). C(11)-LAS sorption from activated sludge appeared to be partially reversible in river water, while a marked hysteresis phenomenon was observed for azocasein and azoalbumin, implying a low degree of reversibility in their exchange between activated sludge and river water. It has also been displayed that the conductivity variation of bulk water (comprised between 214 and 838 microS cm(-1)) exerted no dramatic effect on the C(11)-LAS desorption from activated sludge flocs, while a little effect of it on azocasein desorption was observed. Thus, biological aggregates as activated sludge flocs can serve as an intermediate carrier for C(11)-LAS, while it represents a sink for proteins.     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Fenton-聚硅铝铁硼处理生活垃圾压滤液研究

以正交设计方法为基础，以COD去除率为指标，确定了聚硅铝铁硼（PSAFB）最优制备条件，研究了Fenton-PSAFB混凝法处理城市生活垃圾压滤液的最优反应条件和处理效果。结果表明：以200 mL生活垃圾压滤液为处理对象，复合絮凝剂PSAFB的最优制备工艺条件为：Al/Si为1/2，Fe/Si为1/2，B/Si为1/6；其最优反应条件为：pH值为5.0，投加量为200 mg/L（以SiO₂计)；Fenton法最优反应条件为：pH值为3.0，30%H₂O₂为20 mL，1 mol/L FeSO₄为30 mL；采用最优反应条件的Fenton-PSAFB处理垃圾压滤液，浊度去除率达到95.2%，COD去除率达到84.2%，BOD₅去除率达到81.5%。     

The gas phase addition of NOx to olefins

The addition of N₂O₅ to 1-hexene in synthetic air results in 1,2-hexanedioldinitrate and 2-hexanon-1-ol-nitrate as the main products and some -hydroxy-1-ol-nitrate. In the reaction with cyclohexene, cis/trans-1,2-cyclohexanediol-dinitrate and cyclohexene-1-on-2-ol-nitrate have been detected. The addition of NO₃ to isoprene produces 4-nitrato-3-methylbutenal-2. The reaction of NO₃ with methylenecyclohexane and sabinene in air results in 1-(methylnitrate) cyclohexane-1-ol and both epimers of 1-(methylnitrate)-4-(isopropyl) cyclo-hexene-4-ol, respectively. The main products of the addition of NO₃ to - and β-pinene were probably rearranged compounds of the limonene type: -pinene produces 1-(methyl)-2-(nitrato)-4-(2-propane-2-ol)-cyclohex-1-ene and β-pinene produces 1-(methylnitrate)-4-(2-propane-2-ol)cyclohex-1-ene. Other rearrangements give rise to a variety of nitrates and ketonitrates of structures as yet unknown in the - and β-pinene systems.

The probably particle-borne addition of NO₂ to -pinene, β-pinene and camphene in air produces 2-nitrolimonene, 7-nitrolimonene and nitrocamphene as the main reaction products.     

Mercury induced alterations in the intestinal,absorption of nutrients in the fresh water murrel, Channapunctatus

The effect of five concentrations (10 mM, 1 mM, 0.1 mM, 0.01 mM and 0.001 mM) of mercury on the rate of absorption of glucose, fructose, glycine and tryptophan by the intestine of the fresh water murrel $\text{Channa}$$\text{punctatus}$ has been studied. Intestinal absorption of these nutrients was also examined in fish exposed to a sublethal concentration (3 μg/l) of mercury for 15 and 30 days. Significant decrease was recorded in the rate of intestinal absorption of all the four nutrients with higher concentrations (10 mM, 1 mM and 0.1 mM) of mercury. 0.01 mM and 0.001 mM of mercury also reduced the transport rate but it was insignificant, except in case of tryptophan, where 0.01 mM of mercury also produced significant decrease. Exposure of fish by bath to mercury also resulted in significant decrease in the intestinal transport rate of all the four nutrients after 30 days.     

Oxidative dealkylation of five phenylurea herbicides by the fungus CunninghamellaechinulataThaxter

Microorganisms isolated from soil degrade phenylurea herbicides via two major pathways: (i) direct hydrolysis by an amidase leading to N,O-dimethylhydroxylamine, CO₂ and aniline¹ and (ii) N-dealkylation, which has been described as the first step in urea herbicide degradation by a variety of organisms including mammals, plants and microbial systems (for a review see reference 2).Until now no attempts have been made to investigate the mechanism of N-demethylation of substituted ureas in soil microorganisms, due to the instability of the N-hydroxymethyl intermediates. This reaction mechanism has only been described in detail in green plants^3–5. As among soil fungi Phycomycetes are known to demethylate phenylurea herbicides^6,7 this study has been made to identify intermediate hydroxymethyl compounds from urea herbicides, when incubated with the fungus $\text{Cunninghamella echinulata Thaxter}$.     

Regulatory effects of dioxin-like and non-dioxin-like PCBs and other AhR ligands on the antioxidant enzymes paraoxonase 1/2/3

Paraoxonase 1 (PON1), an antioxidant enzyme, is believed to play a critical role in many diseases, including cancer. PCBs are widespread environmental contaminants known to induce oxidative stress and cancer and to produce changes in gene expression of various pro-oxidant and antioxidant enzymes. Thus, it appeared of interest to explore whether PCBs may modulate the activity and/or gene expression of PON1 as well. In this study, we compared the effects of dioxin-like and non-dioxin-like PCBs and of various aryl hydrocarbon receptor (AhR) ligands on PON1 regulation and activity in male and female Sprague-Dawley rats. Our results demonstrate that (i) the non-dioxin-like PCB154, PCB155, and PCB184 significantly reduced liver and serum PON1 activities, but only in male rats; (ii) the non-dioxin-like PCB153, the most abundant PCB in many matrices, did not affect PON1 messenger RNA (mRNA) level in the liver but significantly decreased serum PON1 activity in male rats; (iii) PCB126, an AhR ligand and dioxin-like PCB, increased both PON1 activities and gene expression; and (iv) even though three tested AhR ligands induced CYP1A in several tissues to a similar extent, they displayed differential effects on the three PONs and AhR, i.e., PCB126 was an efficacious inducer of PON1, PON2, PON3, and AhR in the liver, while 3-methylcholantrene induced liver AhR and lung PON3, and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), the most potent AhR agonist, increased only PON3 in the lung, at the doses and exposure times used in these studies. These results show that PCBs may have an effect on the antioxidant protection by paraoxonases in exposed populations and that regulation of gene expression through AhR is highly diverse.     

UV/ozone degradation of gaseous hexamethyldisilazane (HMDS)

As a carcinogen, hexamethyldisilazane (HMDS) is extensively adopted in life science microscopy, materials science and nanotechnology. However, no appropriate technology has been devised for treating HMDS in gas streams. This investigation evaluated the feasibility and effectiveness of the UV (185+254nm) and UV (254nm)/O(3) processes for degradation of gaseous HMDS. Tests were performed in two batch reactors with initial HMDS concentrations of 32-41mgm(-3) under various initial ozone dosages (O(3) (mg)/HMDS (mg)=1-5), atmospheres (N(2), O(2), and air), temperatures (28, 46, 65 and 80 degrees C), relative humilities (20%, 50%, 65%, 99%) and volumetric UV power inputs (0.87, 1.74, 4.07 and 8.16Wl(-1)) to assess their effects on the HMDS degradation rate. Results indicate that for all conditions, the decomposition rates for the UV (185+254nm) irradiation exceeded those for the UV (254nm)/O(3) process. UV (185+254nm) decompositions of HMDS displayed an apparent first-order kinetics. A process with irradiation of UV (185+254nm) to HMDS in air saturated with water at temperatures of 46-80 degrees C favors the HMDS degradation. With the condition as above and a P/V of around 8Wl(-1), k was approximately 0.20s(-1) and a reaction time of just 12s was required to degrade over 90% of the initial HMDS. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254nm) were found to be caused by OH free-radical oxidation produced from photolysis of water or O((1)D) produced from photolysis of oxygen. The economic evaluation factors of UV (185+254nm) and UV (254nm)/O(3) processes at different UV power inputs were also estimated.     

Measurement of 13C/12C of chloroacetic acids by gas chromatography/combustion/isotope ratio mass spectrometry

This paper describes a novel analytical methodology using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) to measure the 13C/12C ratios of chloroacetic acids (CAAs). CAAs are a major class of environmental pollutants that are widely distributed throughout the world, often at relatively high concentrations, and are of concern due to their toxic effects, particularly on plants. The 13C/12C of CAA reagents was measured by IRMS subsequent to offline combustion. Aqueous solutions of these CAAs were derivatized to the corresponding methyl chloroacetates (MCAAs) with acidic methanol with a known isotopic composition, extracted into pentane, and analyzed by GC/C/IRMS. Measured 13C/12C ratios of derivatized MCAAs were in agreement with calculated values within 1 per thousand for monochloroacetic acid and trichloroacetic acid and within 2 per thousand for dichloroacetic acid, suggesting that methylation and other analytical methodology steps do not isotopically fractionate derivatized MCAAs. 13C/12C ratios of reagent CAAs from different sources had varying isotopic signatures suggesting differences in source carbon and/or production methods. Our results underscore the potential of stable isotopes to serve as tracers of environmental sources of CAAs.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

UV/H_2O_2/TiO_2联合水解酸化+MBR工艺处理亚砜废水

二甲基亚砜(DMSO)废水因其COD高、可生化性差的特性而较难处理。本实验以采用硫酸二甲酯法生产DMSO的某化工厂废水为研究对象,设计并建立了组合式光催化氧化装置联合水解酸化+MBR工艺的中试系统,探讨了组合式光催化氧化装置、氧化剂投加量、pH、反应时间和水力停留时间对系统处理效果的影响。结果表明,组合式光催化氧化装置可有效提高DMSO废水的可生化性。最优工艺参数为:按H2O2与原水COD质量浓度比为2∶1投加H2O2,在pH值为4、反应时间为6 h、水力停留时间为4 h的条件下,该系统对原水COD(5 000 mg/L)去除率大于98%,出水COD达到《污水综合排放标准》(GB 8978-1996)一级要求。     

Complete dechlorination of DDE/DDD using magnesium/palladium system.

Kinetic studies on the dechlorination of 1,1-dichloro-2,2 bis (4,-chlorophenyl) ethane (DDD) and 1,1,dichloro-2,2 bis (4,-chlorophenyl) ethylene (DDE) in 0.05% biosurfactant revealed that the reaction follows second-order kinetics. The rate of reaction was dependent on the presence of acid, initial concentrations of the target compound, and zerovalent magnesium/tetravalent palladium. Gas chromatography-mass spectrometry analyses of DDE dechlorination revealed the formation of a completely dechlorinated hydrocarbon skeleton, with diphenylethane as the end product, thereby implying the removal of all four chlorine atoms of DDE. In the case of DDD, we identified two partially dechlorinated intermediates [namely, 1,1-dichloro-2, 2 bis (phenyl) ethane and 1, chloro-2, 2 bis (phenyl) ethane] and diphenylethane as the end product. On the basis of products formed from DDD dehalogenation, we propose the removal of aryl chlorine atoms as a first step. Our investigation reveals that biosurfactant may be an attractive solubilizing agent for DDT and its residues. The magnesium/palladium system is a promising option because of its high reactivity and ability to achieve complete dechlorination of DDE and DDD.     

Bioaccumulation of pentachlorophenol by killifish (Fundulussimilus)

Killifish ($\text{Fundulus}$$\text{similis}$) were exposed in the laboratory to pentachlorophenol (PCP) at concentrations of 57 to 610 μg PCP/L. Bioaccumulation reached a plateau value of about 53 by 168 hrs and remained at this level for at least 72 hrs. One-half the plateau value was reached in about 25 hrs. Following exposure, fish placed in PCP-free aquaria lost PCP rather slowly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.7}\text{days}$). The depuration data were suggestive of a pool of PCP which was lost more rapidly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.2}\text{hrs}$). The results of this study are compared to similar studies in other species. The bioaccumulation factors measured in this study agree relatively well with those in other marine species, but are lower than reported for fresh water species. Possible reasons for this difference are discussed.     

Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.