Sonochemical decomposition of phenol: evidence for a synergistic effect of ozone and ultrasound for the elimination of total organic carbon from water

Advanced oxidation processes (AOPs) for water and wastewater treatment are often handicapped by their inability to completely eliminate total organic carbon (TOC). In order to explore the capability of the combination of ultrasonic irradiation with ozone for the rapid removal of TOC, we examined the degradation rates of dissolved phenol (C6H5OH) in water with high-frequency ultrasound over the range of 200-1000 kHz, with ozone and with the combined application of sonication and ozonation. When ozone and ultrasound are applied simultaneously, a pronounced synergistic effect is observed that leads to the complete and rapid elimination of TOC at enhanced reaction rates. At longer reaction times, phenol oxidation by 03 leads to oxalate and formate, which accounts for the majority of the residual TOC. However, the combination of US (ultrasound) and ozone together readily oxidizes HCO2- and C2O4(2-) to CO2 while they prove to be relatively resistant to further oxidation to CO2 by O3 alone.     

等碳量添加不同有机物料对土壤有机碳组分及土壤呼吸的影响

为探明不同有机物料对土壤有机碳组分和呼吸速率的影响,研究了等碳量添加生物炭、秸秆、生物炭+秸秆条件下烤烟生长过程中土壤总有机碳（TOC）、易氧化有机碳（ROC）、可溶性有机碳（DOC）、微生物量碳（MBC）含量及土壤呼吸速率的动态变化,分析了土壤各有机碳组分之间及其与土壤呼吸速率的关系。研究结果显示,与单施化肥相比,等碳量添加有机物料后土壤各有机碳组分含量以及土壤呼吸速率均显著提高;添加有机物料的3个处理中,单施生物炭处理土壤TOC含量最高,CO₂排放量最低;单施秸秆处理土壤活性有机碳（AOC）占TOC的比例及CO₂排放量最高,但TOC含量最低;生物炭+秸秆处理土壤TOC含量显著高于添加秸秆处理,AOC含量显著高于单施生物炭处理,且CO₂排放量显著低于单施秸秆处理。土壤ROC、DOC、MBC之间关系密切,三者与土壤呼吸速率均呈显著正相关。由此可见,等碳量添加有机物料条件下,生物炭有利于土壤有机碳的固存,可减少CO₂的排放,但短期内对提高土壤AOC的效果不如秸秆直接还田明显,而秸秆直接还田对土壤AOC含量的提升效果最好,但会增加CO₂的排放,两者配施既提高了土壤AOC的含量,又减少了CO₂的排放。      

Factors affecting the efficiency of carbon monoxide photoproduction in the St. Lawrence estuarine system (Canada)

This study examined the effects of water temperature and the origin (terrestrial vs marine) and light history of chromophoric dissolved organic matter (CDOM) on the apparent quantum yields of carbon monoxide (CO) photoproduction for water samples collected along a salinity gradient (salinity range: 0-33) in the St. Lawrence estuarine system (Canada). The solar insolation-weighted mean apparent quantum yield of CO (phico) decreased as much as fourfold with increasing salinity and showed a strong positive correlation with the dissolved organic carbon-specific absorption coefficient at 254 nm. This suggests that terrestrial CDOM is more efficient at photochemically producing CO than is marine algae-derived CDOM and that aromatic moieties are likely involved in this photoprocess. CDOM photobleaching, mainly at the very early stage, dramatically decreased phico (by up to 6.4 times) for low-salinity samples, but photobleaching had little effect on the most marine sample. For a 20 degree C increase in temperature, phico increased by approximately 70% for low-salinity samples and 30-40% for saline samples. This study demonstrates that water temperature, as well as the CDOM's origin and light history, strongly affect the efficiency of CO photoproduction. These factors should be taken into account in modeling the photochemical fluxes of CO and other related CDOM photoproducts on varying spatiotemporal scales.     

Sorption and degradation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine in soil

The sorption/desorption and long-term fate of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was examined using sterilized and nonsterilized soils. Two soils were used that differ mainly by the amount of total organic carbon (TOC): an agricultural topsoil (VT, 8.4% TOC) and a sandy soil (SSL, 0.33% TOC). The adsorption isotherms performed at room temperature were well-described by a linear model, which led to sorption distribution coefficients of 2.5 and 0.7 L kg(-1) for VT and SSL soils, respectively. The organic content of soil did not significantly affect HMX sorption. Over a period of 20 weeks, HMX degraded (60% disappearance) in static anaerobic nonsterile VT soil preparations. In separate experiments using UL-[14C]-HMX, 19% mineralization (liberated 14CO2) was obtained in 30 weeks. In addition, four nitroso derivatives of HMX were detected. Knowing the sorption/desorption behavior and the long-term fate of HMX in soil will help assess the effectiveness of natural attenuation for HMX removal.     

铁改性聚丙烯腈纳微米纤维催化剂在偶氮染料降解中的应用

利用静电纺丝法制备聚丙烯腈（PAN）纳米纤维,应用偕胺肟改性PAN纳米纤维（AO-n-PAN）与FeCl3反应得到PAN纳米纤维铁配合物（Fe-AO-n-PAN）,并使用SEM和FTIR对其进行表征。最后将Fe-AO-n-PAN作为非均相光催化剂应用于偶氮染料C.I.活性红195（RR 195）的氧化降解反应中;考察催化剂中铁离子含量（QFe-PAN）,辐射光强度和H2O2初始浓度等因素对其催化活性的影响,并使用紫外可见光谱和总有机碳（TOC）对染料的氧化降解反应进行分析。结果表明：AO-n-PAN中的偕胺肟基团与铁离子发生配位反应,增加AO-n-PAN中的偕胺肟基团数目能制备出高QFe-PAN的Fe-AO-n-PAN。Fe-AO-n-PAN中QFe-PAN的增加和辐射光强度的增大都可以显著提高RR 195的降解速率,当H2O2为3.0 mmol/L时Fe-AO-n-PAN催化活性较高。Fe-AO-n-PAN不仅对染料分子中的偶氮键和芳香环结构具有催化作用,而且还能够使其转化为无机物。     

Impact of simulated solar irradiation on disinfection byproduct precursors

The Sacramento-San Joaquin Delta is the major drinking water source for 23 million California residents. Consequently, many studies have examined disinfection byproduct (DBP) formation in relation to Delta dissolved organic carbon (DOC) concentration. However, DOC characteristics within the Delta are not the same as those entering downstream water treatment facilities. As water is transferred to Southern California through the California Aqueduct, a 714.5 km-open channel, it is exposed to sunlight, potentially altering DBP precursors. We collected water from three sites within the Delta and one nearthe California Aqueduct, representing different DOC sources, and irradiated them in a solar simulator at a dose equivalent to that received during four days conveyance in the aqueduct. Photolytic changes in DOC were assessed by measuring CO2 and organic acid production, fluorescence, and ultraviolet absorbance over time. Trihalomethane (THM) and haloacetic acid (HAA) formation potentials, as well as the distribution of hydrophobic, transphilic, and hydrophilic acid fractions were determined at exposures equivalent to one and four days. Solar irradiation significantly decreased ultraviolet absorbance and fluorescence intensity, produced organic acids, and increased the hydrophilic fraction of waters. These changes in DOC caused a shift in bromine incorporation among the THM and HAA species. Our results are the first to demonstrate the importance of sunlight in altering DOC with respect to DBP formation.     

Optimizing municipal solid waste combustion through organic and elemental carbon as indicators

The temperature, redox conditions, and residence times of the solid waste on the grate and of the raw gas in the secondary combustion zone determine the mineralization processes of organics in municipal solid waste incinerators. An improved knowledge of the influence of these factors on the incineration process might help to optimize incinerators with regard to mineralization efficiency of organics. This paper presents a method for investigating the influence of process parameters on mineralization of organics to CO2 by using the elemental carbon (EC) and organic carbon (OC) concentrations in the solid residues as indicators. The results obtained by experiments in full-scale incinerators show that the EC concentration in these residues is a good indicator of oxygen supply, whereas the OC/EC ratio is a good indicator of temperature in and above the furnace bed. Very effective burnout of the bottom ash up to 0.95 g of TOC (EC + OC) per kilogram of dry matter (DM) and of the electrostatic precipitator (ESP) ash up to 0.24 g of TOC per kilogram of DM was achieved in a full-scale incinerator.     

Thermal oxidation kinetics and mechanism of sludge from a wastewater treatment plant

The organic fraction of a sludge from a wastewater biological treatment plant is characterized by the total organic carbon, TOC, content, cyclohexane and toluene extractions, and thermal desorptions in nitrogen and air flow at different temperatures. The inorganic fraction is characterized by water extraction, FT-IR spectroscopy, thermogravimetric analysis, and scanning electron microscopy/energy dispersion X-ray analysis. The thermal degradation rate of organic carbon is studied in batch experiments in air, in the 250-500 degrees C temperature range. The sample TOC is used to measure the decrease of reagent concentration with time. The TOC vs time data are well fitted by a generalized kinetic model, previously proposed for the MSWIs fly ash thermal degradation. The rate constants of the immediate carbon gasification, k2, and of the dissociative oxygen chemisorption, k1, followed by C(O) intermediate gasification, k3, together with activation and thermodynamic parameters are calculated. The rate determining step is the C(O) oxidation. The influence of desorbed or extracted organic compounds on kinetics and the role of the C(O) formation in explaining the reaction mechanism as well as the comparison with fly ash kinetics are discussed.     

河南烟区土壤有机碳组分特征及其对烟叶化学成分的影响

为了明确河南典型烟区土壤有机碳库组分特征及其对烟叶化学成分含量(质量分数)的影响,采集分析了河南许昌、平顶山、洛阳和三门峡4个典型植烟区的土壤和烟叶样品.结果表明:①河南产区土壤总有机碳(TOC)、活性有机碳(AOC)、颗粒有机碳(POC)和溶解性有机碳(DOC)含量分布范围在3.72～13.80、0.26～0.74、...     

Semiconductor-mediated Photocatalyzed degradation of a herbicide derivative, chlorotoluron, in aqueous suspensions

The photocatalytic degradation of a herbicide derivative, chlorotoluron [3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 1], has been investigated in aqueous suspensions of titanium dioxide (TiO2) under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics of the model compound was investigated under different conditions such as type of TiO2, pH, catalyst concentration, substrate concentration, temperature, and in the presence of different electron acceptors such as hydrogen peroxide (H2O2), potassium persulfate (K2S2O8), and potassium bromate (KBrO3) besides molecular oxygen. TiO2 Degussa P25 was found to be a more efficient photocatalyst for the degradation of the model compound as compared with other photocatalysts. The degradation products were analyzed using GC/MS analysis technique and probable pathways for the formation of different products have been proposed.     

Organic pollutant removal versus toxicity reduction in industrial wastewater treatment: the example of wastewater from fluorescent whitening agent production

Industrial wastewater treatment in the chemical industry aims at eliminating organic contaminants, as these pollutants may be persistent and ecotoxic. In a case study performed in collaboration with the chemical industry, we investigated the removal of a fluorescent whitening agent and its side products in the wastewater-treatment system. Adsorption to activated carbon and biological treatment were simulated in laboratory tests. Algae toxicity tests were performed to quantify the toxicity of the wastewater mixture and of single components. The contaminants identified accounted for up to 82% of the wastewater's total organic carbon (TOC). Adsorption to activated carbon eliminated the TOC and the single contaminants only slightly. Nevertheless, the toxicity of the wastewater decreased by 40%. In contrast, biological treatment reduced the TOC by up to 80%, and the whole effluent toxicity increased. These results indicate that new ecotoxic metabolites were formed during the biological treatment. They also illustrate that mere reduction of the TOC in the wastewater-treatment system is not sufficient for ensuring a reduction of environmental impact. Therefore, simultaneously conducting TOC measurements and toxicity tests, as demonstrated in the current work, is recommended.     

Photooxidation and its effects on the carboxyl content of dissolved organic matter in two coastal rivers in the southeastern United States

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.     

Enhanced sonocatalytic degradation of azo dyes by Au/TiO2

Au-loaded TiO2 (Au/TiO2) has been reported for the first time as a sonocatalyst. It was found that the catalyst Au/TiO2, with a low Au loading 0.5 wt % and under common and commercial frequency (40 kHz) ultrasonic irradiation, greatly accelerated both the discoloration and total organic carbon (TOC) removal of azo dyes such as orange II (Org II), ethyl orange (EO), and acid red G (ARG), as compared to bare TiO2 and nano-Au catalyst. About 80% TOC removal was achieved after complete discoloration of 2.5 x 10(-4) M Org II. H2O2 and H2 formation as well as their accumulation was greatly enhanced due to Au loading on TiO2. Both oxidative and reductive degradation intermediates have been detected, and thus the mechanism involves both enhanced oxidation and enhanced reduction via the accelerated formation of active *OH and *H radicals due to Au loading on TiO2, which is supported by electron spin resonance (EPR) and other evidence. The study provides an admirable way to raise the efficiency of sonication and to treat azo dye-containing wastewaters with sonocatalytic processes.     

不同秸秆对植烟土壤有机碳矿化和腐殖质组成的影响

针对南方常见的烤烟轮作体系,研究添加不同作物秸秆（烟草、油菜和水稻）后土壤有机碳矿化特征和腐殖物质含量变化,为合理利用烟田废弃物提供理论依据。采用室内恒温培养试验,将3种秸秆分别以覆盖于土壤表层和与土壤混匀2种方式添加,分析不同处理土壤CO₂释放规律、总有机碳（TOC）和腐殖物质含量的变化与相关性。结果表明,以不同方式添加作物秸秆对土壤CO₂释放影响显著,覆盖处理土壤有机碳矿化强度高于混匀处理,达到极显著差异;3种秸秆的添加均能显著提高土壤CO₂释放速率和累积释放量,有机碳矿化强度表现为油菜秸秆 > 烟草秸秆 > 水稻秸秆。经过180 d的培养,添加秸秆的各处理土壤TOC、腐殖物质各组分含量和PQ值显著升高。相关性分析表明,土壤CO₂累积释放量与土壤中TOC、HE（可提取腐殖质总量）与FA（富里酸）含量呈显著相关。因此,3种作物秸秆的添加可提高植烟土壤有机碳含量和腐殖化程度,且秸秆混匀处理具有较好的固碳减排效果。     

Kinetics of Solids Leaching During Rehydration of Particulate Dry Vegetables

ABSTRACT: Air-dried and freeze-dried carrots were rehydrated in a computerized mixing system, and the medium was analyzed for sugar content with high-performance liquid chromatography (HPLC) and for total organic carbon (TOC). Leaching of solids was significant at very short rehydration time. Understanding the mechanism of the leaching process could provide information required for simulation. TOC values were significantly higher than those derived by HPLC, indicating that other organic components were extracted. The difference between TOC and HPLC values varied with time, indicating the existence of a different mass transfer rate. Sugars and TOC values followed an exponential behavior. Quantifying solids leaching is important for modeling and simulation of the rehydration process and for product optimization.     

Fat Content Influences the Color, Lipid Oxidation, and Volatiles of Irradiated Ground Beef

ABSTRACT:  Ground beef with 10%, 15%, or 20% fat were added with none, 0.05% ascorbic acid + 0.01%α-tocopherol, or 0.05% ascorbic acid + 0.01%α-tocopherol + 0.01% sesamol, and irradiated at 0 or 2.5 kGy. The meat samples were displayed under fluorescent light for 14 d at 4 °C. Color, lipid oxidation, volatiles, oxidation-reduction potential (ORP), and carbon monoxide (CO) production were determined during storage. Irradiation increased lipid oxidation and total volatiles of ground beef regardless of fat contents. Ascorbic acid +α-tocopherol + sesamol treatment was the most effective in reducing lipid oxidation during storage. The production of ethanol in nonirradiated ground beef increased dramatically after 7 d of storage due to microbial growth. Total aldehydes and hexanal increased drastically in irradiated control over the storage period, but hexanal increased the most by irradiation.  L *-values was decreased by irradiation, but increased in all meat regardless of fat contents as storage period increased. Irradiation reduced the redness, but fat contents had no effect on the  a *-value of ground beef. Sesamol lowered, but ascorbic acid +α-tocopherol maintained the redness of irradiated beef up to 2 wk of storage. The yellowness of meat was significantly decreased by irradiation. The reducing power of ascorbic acid +α-tocopherol lasted for 3 d, after which ORP values increased. Irradiation increased CO production regardless of fat content in ground beef. In conclusion, up to 20% fat had no effect on the quality change of irradiated ground beef if ascorbic acid +α-tocopherol was added.     

Seasonal effects on the physicochemical characteristics of fish sauce made from capelin (Mallotus villosus)

Fresh capelin (Mallotus villosus) was harvested from the North Atlantic during both summer and winter fishing seasons. Reaction conditions for fish sauce processing were optimized with respect to temperature, salt concentration and reaction time, using a response surface methodology (RSM) experimental design. Whole capelin was minced and samples were ground with increasing salt concentrations. RSM optimizations were conducted, ranging from 5% to 30% salt, and incubating at 5° intervals from 0 to 65 °C. Autolytic activity was estimated by extracting the liquid formed by the mixture with trichloroacetic acid and estimating protein content by the Lowry method. Samples for fish sauce production were then prepared under optimized conditions by mixing ground capelin with 10% salt and incubating at 50 °C for up to 270 days for the summer capelin and up to 360 days for the winter capelin. Samples were collected at regular intervals and analyzed for liquid yield, moisture, protein, soluble solids, specific gravity, pH, colour and amino acid content. Kjeldahl protein content in the fish sauce from summer capelin was 2.03% after 250 days of fermentation and twice as high as that in winter capelin fish sauce. Moisture content and pH were lower in the summer capelin fish sauce, but Brix and density were higher than those in fish sauce from winter capelin. Brown colour formation was very rapid in the summer capelin fish sauce but slow in the winter capelin fish sauce. Summer capelin may be successfully utilized for the production of fish sauce without added enzymes.     

Isotopic constraints on the fate of petroleum residues sequestered in salt marsh sediments

To provide a new perspective on the fate of petroleum in the marine environment, we utilized variations in the natural abundance of radiocarbon (14C) to detect and quantify petroleum residues that have persisted in Wild Harbor sediments, West Falmouth, MA, for more than 30 years. The 5730-yr half-life of 14C makes this isotope ideal for the detection of fossil-fuel-derived contaminants (14C free) within different fractions of natural organic matter (modern 14C content) in environmental matrixes. Samples of both contaminated and uncontaminated sediments were sequentially treated, first by solvent extraction, followed by saponification, and then acid hydrolysis. Radiocarbon analysis of the sediment residues and select extracts was performed to probe for the presence of fossil fuel contaminants and/or their metabolites in different pools of sedimentary organic matter. Our results indicate that the majority of fossil carbon is solvent-extractable and has not been incorporated in the insoluble organic matter in sediment. Unextracted sediments contaminated with petroleum contain significantly less 14C than extracted sediments, and isotope mass balance calculations suggest that up to approximately 9% of the total organic carbon (TOC) in the petroleum contaminated sediment horizons is derived from solvent-extractable petroleum. These estimates are similar to values calculated when the total quantities of oil (measured by gas chromatography with flame ionization detector (GC-FID)) are compared to TOC content (determined by elemental analysis). These results pave the way for applications of this isotopic approach to more complex environmental systems where the fate of contaminants is less certain.     

Chemical investigation of eight different types of carbonaceous particles using thermoanalytical techniques

The chemical composition of ambient aerosol particles affects numerous important aerosol parameters such as their hygroscopicity, optics, and mass as well as their potentially adverse health effects. The objective of this study was to derive both detailed chemical speciation and useful proxies for the quantitative classification of the organic matter (OM) content of carbonaceous aerosol samples. Using three different thermal desorption techniques in an inert atmosphere we investigated eight different carbonaceous particulate matter (PM) samples used for health effect studies: thermal desorption gas chromatography with mass spectrometry, evolved gas analysis with mass spectrometry, and thermogravimetry with Fourier transform infrared spectroscopy. The samples include different types of laboratory-generated particles (pigment black, diffusion flame soot, spark-generated carbon) and two ambient aerosol samples (diesel soot and particulates collected in a road tunnel). All samples showed increasing mass desorption with rising temperature, but no reliable OM classification was possible based on thermal mass desorption alone. In fact, the "organic-free" spark-generated carbon particles showed the second highest mass desorption at 800 degrees C due to the formation of oxygenated structures on unsaturated surface sites and the subsequent evolution of CO and CO2 at elevated temperatures. A quantitative OM classification was accomplished by combining measurements of thermogravimetry and mass spectrometry (up to 800 degrees C) into a novel parameter, the "apparent organic mass fraction". The validity of this classification was confirmed with a second proxy parameter, based only on the evolution of organic components during thermal desorption and information on the generation process of the particles. Both types of pigment blacks (Printex) samples and the spark-generated carbon particles showed the lowest apparent organic mass fraction (< 5%), whereas for road tunnel and diesel emission particles < 16 and < 19% was estimated, respectively.     

Mechanism of the photocatalytic degradation of C.I. Reactive Black 5 at pH 12.0 using SrTiO3/CeO2 as the catalyst

The photocatalytic degradation mechanism of an azo dye, C.I. Reactive Black 5 (RB5), has been investigated in an aqueous suspension of SrTiO3/CeO2 composite under 250 W UV irradiation at pH 12.0. The process was studied by monitoring the change in RB5 concentration and the intermediate products employing UV-visible spectrophotometry, ion chromatography (IC), and gas chromatography/ mass spectrometry (GC/MS) techniques and depletion in total organic carbon (TOC) content as a function of irradiation time. The adsorption peaks at wavelengths of 600, 312, and 254 nm were identified as the chromophore structure, and the naphthalene and benzene components of RB5, respectively. Little influence of iodide ion, tert-butyl alcohol, fluoride ion, or persulfate ion as h(vb)+, *OH, or e(cb)- scavengers on the decolorization proved that the decolorization of RB5 primarily proceeded by photolysis and/or O2*- in the bulk solution. After the decolorization, the process could shift progressively from the bulk solution to the surface of the catalysts and cleavage of the naphthalene and benzene rings was mainly attributed to the h(vb)+ pathway and *OH(ads) reactions, which was further verified by the effect of scavengers.