Decomposition of chlorinated dioxins, odourous compounds and NOx from MSW incineraton plant by oxidizing catalyst

An experiment was carried out to decompose chlorinated dioxins (PCDDs, PCDFs) Chlorobenzenes, NOx and odourous compounds (H₂S, CH₄S, C₂H₆S₂, C₈H₈, C₂H₆S, C₂H₄O, NH₃) simultaneously using a catalyst in the MSW incineration plant. The experiments were conducted at temperatures from 200°C to 400°C and from 3000h⁻¹ to 6000h⁻¹ at space velocity. A catalyst containing V₂O₅ and WO₃ on the basis of TiO₂ is used, an oxidizing catalyst of the honeycomb type. The average decomposition efficiencis were 95%, 98%, 92% for PCDDs(48CDDs), PCDFs(48CDFs) and Chlorobenzenes(36CLBs) at a reaction temperature of 350°C and a space velocity of 3000h⁻¹, more than 90% for NOx at a reactiont temperature of 300°C and more than 80% for odourous compounds at the reaction temperature of 300°C and a space velocity of 6000h⁻¹. All those compounds were decomposed successfully with increasing contact time and surface. The rate-determing step was the chemical reaction of catalyst surface.     

Comparative study of the oxidation of atrazine and acetone by H2O2/UV, Fe(III)/UV, Fe(iii)/H2O2/UV and Fe(II) or Fe(III)/H2O2

In this study, the rates of degradation of organic compounds by several AOPs (H₂O₂/UV, Fe(III)/UV, Fe(III)/H₂O₂/UV, Fe(II)/H₂O₂ and Fe(III)/H₂O₂) have been compared. Experiments were carried out at pH ≈ 3 (perchloric acid / sodium perchlorate solutions) and with UV reactors equipped with a low-pressure mercury vapour lamp (emission at 253.7 run). The data obtained with atrazine ([Atrazine]_o = 100 μg/L) showed that the rate of degradation of atrazine in very dilute aqueous solution is much more rapid with Fe(III)/UV than with H₂O₂/UV. Photo-Fenton process (Fe(III)/H₂O₂/UV) was found to be more efficient than H₂O₂/UV and Fe(II)/H₂O₂ for the mineralization of acetone ([Acetone]_o = 1 mM).     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons

The temporal variability and bioaccumulation dynamics of C_12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C_12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g⁻¹, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g⁻¹) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C_15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against K_ow showed a parabolic pattern maximizing at n-C_14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K_ow: 7.2–9.9), intermediate-size C_14–18 n-alkanes and C_15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C₂₅ to above 90% for n-C_14–15 and isoprenoids.     

湖北省能源消费CO2与大气污染物协同减排研究

以2015年为基准年,基于拓展的STIRPAT模型预测2025年湖北省能源消费CO2和主要大气污染物排放量.通过设置基准(记为BAU)情景、低碳(记为LC)情景和强化低碳(记为ELC)情景3种控制情景,测算CO2和主要大气污染物的减排量,并运用污染物减排量交叉弹性法评价了CO2减排对主要大气污染物的协同效应.结果表明,...     

贵阳市污染源PM2.5中铂族元素的分布特征

为掌握贵阳市污染源PM2.5中铂族元素(PGE)的分布特征,采集7类主要污染源42个PM2.5样品,采用同位素稀释/电感耦合等离子体质谱法定量测定PGE中铂(Pt)、钯(Pd)、铑(Rh)的含量.结果表明:(1)金属冶炼尘PM2.5中Pt、Pd、Rh平均值分别为2186.136、1239.827、346.172 ng/...     

Photodegradation of surfactants. XV: Formation of SO4 ions in the photooxidation of sulfur-containing surfactants

Three types of surfactants and related reference compounds containing sulfonate (-SO₃Na), sulfate (-OSO₃Na) or thioether carboxylate (-S-Cn-COOK) group were photodecomposed in an aqueous heterogeneous dispersion system. The photomineralization to SO₄²⁻ions was examined for the surfactants with different chemical structures. The photocatalytic activities of TiO₂ and ZnO were compared for the sulfonates of dodecylbenzene sulfonate (DBS) and polystyrene sulfonate (PSS), the sulfates of sodium dodecyl sulfate (SDS), and the potassium salts of S-dodecylthioglycol acid (TGA), S-dodecylthiopropionic acid (TPA) and S-dodecylthiomalic acid (TMA). ZnO catalyst exhibited higher activity in the formation of SO₄²⁻ion than TiO₂ catalyst.     

Carbonyls and non-methane hydrocarbons at a rural mountain site in northeastern United States

Measurements of carbonyls and C₂–C₆ non-methane hydrocarbons (NMHCs) were made in ambient air at a rural site at the summit of Whiteface Mountain (WFM) in New York State. Alkanes dominated in the samples, with ethane and propane making up about 55% of the total on a carbon-atom basis. Ethane, the longest-lived of the NMHCs, showed a mixing ratio in the range of 0.86–2.1 ppbv. Photochemical ageing analysis indicated an anthropogenic influence on the NMHC levels. The photochemical reactivity of the hydrocarbons, calculated in terms of propylene-equivalent concentration, was dominated by alkenes (propene and ethene), which accounted for 74% of the total NMHC sum. Air mass back-trajectories have been used to investigate the origin of the observed NMHCs and carbonyls. Higher concentrations were found when air masses arrived from the midwestern US corridor. Acetone was the most abundant species, comprising from 31% to 53% of the total detected carbonyls, followed by MEK (15–53%), HCHO (7–39%), and CH₃CHO (7–19%). Average concentrations were determined to be 1.61 ppbv for CH₃C(O)CH₃, 1.40 ppbv for MEK, 1.16 ppbv for HCHO, and 0.49 ppbv for CH₃CHO. The variations in carbonyl concentrations were observed to follow patterns similar to variations in O₃ concentrations, typical of secondary products. Correlations and statistical analysis of the carbonyls and NMHCs were performed, and showed that most of the compounds derived from mixing and photochemical transformation of long-range transported pollutants from the major source areas. Ranking of the carbonyls with respect to removal of the OH radical showed HCHO to be the most important species, followed by CH₃CHO, MEK, and CH₃C(O)CH₃.     

Processes involved in uptake and release of nitrogen dioxide from soil and building stones into the atmosphere

Atmospheric NO₂ was taken up by samples of various soils and building stones. The NO₂ uptake rate constants were highest in soil samples taken during the summer months. However, the NO₂ uptake rate constants of the soils and building stones were not significantly correlated with any of the following variables: moisture, pH, ammonium, nitrite, or nitrate. NO₂ uptake by soil and stone was not abolished by autoclaving indicating a chemical uptake process. NO₂ uptake by acidic and air-dry soils and stones resulted in nearly stoichiometric reduction of NO₂ to NO. This reduction was enhanced by the addition of ferrous iron and was further enhanced by incubation under 1 ppmv SO₂. The results suggest that NO₂ reduction may be coupled to oxidation of ferrous to ferric iron which may be reduced again by atmospheric SO₂ thus regenerating the ferrous iron content of the soil or stone. Conversion of NO₂ to NO was not observed in neutral or/and moist soils and stones. NO₂ was also taken up by purified and sterilized quartz sand moistend with water. This uptake was enhanced by addition of humic material but not by addition of bacteria which both had been extracted from genuine soil. Under most conditions, only uptake but no release of NO₂ was observed. However, NO₂ was released in air-dry soils that were heated to 45–65°C, or in ammonium-fertilized soil or stone that was drying up at room temperature. Under the latter conditions mimicking field practice, the NO₂ release reached rates that were similar to the NO release rates.     

Association of benzo(a)pyrene with dissolved organic matter: Prediction of Kdom from structural and chemical properties of the organic matter

The affinity of dissolved organic matter (DOM) for binding a polycyclic aromatic hydrocarbon, benzo(a)pyrene (BaP), was measured for 11 surface and ground waters and a commercial humic acid. The hydrophobic-acid (HbA) and hydrophobic-neutral (HbN) compositions of the DOM, solution absorptivity at 270nm (ABS₂₇₀), and DOM molar volumes were determined. Waters enriched in HbA material had a larger molar volume and higher aromatic content (as indicated by the ABS₂₇₀). There was a good correlation between the size and HbA content of the DOM from the different sources and the K_dom for binding BaP. An excellent predictive relationship (r² = 0.9) was demonstrated between the ABS₂₇₀ of a water and the K_dom for binding BaP. Based on these results, it is suggested that binding of BaP to DOM depends not only on the hydrophobicity of DOM, but also on the existence of an open structure within the DOM to provide access of the aqueous solute to hydrophobic domains within the DOM.     

Secondary ozonides of substituted cyclohexenes: a new class of pollutants characterized by collision-induced dissociation mass spectrometry using negative chemical ionization

Recent studies indicate that secondary ozonides of cyclic alkenes are formed in atmospheric reactions and may be relatively stable. The secondary ozonides (SOZs) of cyclohexene (1), 1-methylcyclohexene (2), 4-isopropyl-1-methylcyclohexene (3) and 4-isopropenyl-1-methylcyclohexene (limonene) (4) have been characterized by rapid gas chromatography electron ionization (EI), negative and positive chemical ionization (CI: ammonia, isobutane and methane) and collision-induced dissociation (CID) mass spectrometry. Both EI and positive CI spectra were found unsuitable for reproducible analysis. However, negative CI showed stable (M−H)⁻ ions with minor fragmentation. CID of the (M−H)⁻ ions resulted in simple and reproducible fragmentation patterns for all four SOZs with loss of m/z 18, 44 and 60, tentatively assigned as H₂O, CO₂ and C₂H₄O₂ or CO₃, respectively. Thus, negative CI-MS–MS in combination with rapid gas chromatography is the preferred method for identification of secondary ozonides of cyclohexenes.     

The binding of three PCB congeners to dissolved organic carbon in freshwaters

The binding of three polychlorinated biphenyl (PCB) congeners to natural levels of dissolved organic carbon (DOC) was measured in 12 lakes and streams using Sep-Pak C₁₈ columns. The association coefficients calculated on the basis of DOC (i.e. K_DOC mL/g C), varied by over an order of magnitude among the different freshwaters and ranged between 2.05 × 10² and 8.86 × 10³ mL/g C for PCB 52 and 1.03 × 10⁴ and 1.70 × 10⁵ mL/g C for PCB 153. In general, there were no significant correlations (p > 0.05) between the K_DOC values and various chemical parameters in the study lakes and streams.

A relationship was derived between the fraction of bound PCB and the octanol-water partition coefficient. While this relationship explained almost 50% of the variation in the observed data, it is apparent that other factors influence K_DOC values and that in natural freshwaters, only a small fraction of the DOC is involved in the binding of PCBs and other hydrophobic pollutants.     

天津市挥发性有机物污染特征与来源及其O3生成潜势

为深入了解天津市大气挥发性有机物(VOCs)来源及对O3的影响,基于2020年天津市VOCs在线监测数据,统计分析了VOCs污染特征,用主成分分析法对天津市VOCs的来源进行解析,用最大增量反应活性法分析VOCs的O3生成潜势(OFP).结果表明:2020年天津市VOCs的年均质量浓度总和为56.56μg/m3,其中,...     

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.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

Interlaboratory sampling and analysis of PCDDS and PCDFS in emissions from urban incinerators

Three laboratories participated in a PCDD and PCDF sampling experiment on the stack of a municipal waste incinerator and six laboratories examined a fly ash sample for PCDD_S and PCDF_S in order to assess analytical precision.

The flue gas sampling results are in agreement for the three laboratories and show that the PCDD_S and PCDF_S are predominantly in the gas phase, whereas emitted particulate account for 20% of the total PCDD/PCDF concentration.     

Chlorinated fluorenes and alkylfluorenes in bleached kraft pulp and pulp mill discharges

The occurrence and levels of polychlorinated fluorenes (PCFLs), methylfluorenes (C₁-PCFLs) and dimethylfluorenes (C₂-PCFLs) were studied by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) in hardwood and softwood pulp, effluent and biosludge from a bleached kraft mill. Semiquantitative concentrations of these compounds were estimated using selected ion monitoring and a mass spectral resolution of 10,000. The identification of PCFLs and C₁-PCFLs was confirmed by the chlorination mixtures of fluorene and 2-methylfluorene.

Several congeners were found for each compound groups studied and isomer patterns were similar in bleached pulp and biosludge. The approximated sum levels of di- and trichloro isomers of PCFLs, C₁-PCFLs and C₂-PCFLs in the biosludge were about 2, 5 and 4 ng/g dry weight (dw), respectively. The levels of the corresponding compounds in the softwood pulp were 0.5, 0.8 and 0.2 ng/g dw, respectively. Of the studied compounds, only C₁-diCFLs (0.01 ng/g dw) were detected in the hardwood pulp. In the effluent, PCFLs were non-detectable, but traces of C₁-diCFLs (0.5 ng/L) and C₂-pentaCFLs (0.06 ng/L) were found. These were observed mainly as dissolved in the filtrate and not as particle-bound.     

Composition of torched crude oil organic particulate emitted by refinery and its similarity to atmospheric aerosol in the surrounding area

The absolute contents and relative distributions of organic aerosols [n-alkanes, n-alkanoic and n-alkenoic acids, n-alkan-2-ones and polycyclic aromatic hydrocarbons (PAH)] were determined in torched gases emitted during the crude oil extraction and in the free atmosphere of the Hassi-Messaoud city (Algeria). Monocarboxylic acids, both saturated and monounsaturated (from 9802 to 20 057 ng m⁻³), accounted for the major fraction of the total particulate organic matter identified both in torch exhaust and atmospheric particulate. n-Alkanes were also abundant both in the direct emission (from 460 to 632 ng m⁻³) and city atmosphere (462 ng m⁻³) and displayed a peculiar fingerprint characterised by the presence of a set of branched congeners around even carbon-numbered homologues and a strong even-to-odd predominance along the whole carbon number range (C₁₆–C₃₄). Whilst n-alkan-2-ones were absent in the city and poor in smokes emitted from the torches (from 31 to 42 ng m⁻³), PAH were present at low extents in all sites (from 18 to 65 ng m⁻³). The incomplete thermal combustion of torched crude oil was very likely the main source of these particle-bound organic constituents in the city and its surrounding region.     

UV-H2O2 based AOP and its integration with biological activated carbon treatment for DBP reduction in drinking water

The presence of disinfection byproducts (DBPs) such as trihalomethanes (THMs) and haloacetic acids (HAAs) in drinking water is of great concern due to their adverse effects on human health. Emerging regulation limiting the concentration of DBPs in drinking water has increased demands for technologies and processes which reduce the formation of DBPs in drinking water. In this study, UV-H₂O₂ based advance oxidation process (AOP) was used to treat raw surface water. Experiments were conducted using low pressure mercury vapor UV lamps in collimated beam and flow-through annular photoreactors. The effect of UV fluence (0–3500 mJ cm⁻²) and hydrogen peroxide concentration (0–23 mg l⁻¹) in reducing the concentration of THMs and HAAs was examined. The UV-H₂O₂ AOP was then coupled with a downstream biological activated carbon (BAC) treatment to assess the synergetic benefits of combining the two treatments. It was observed that UV-H₂O₂ AOP was only effective at reducing DBPs at UV fluences of more than 1000 mJ cm⁻²and initial H₂O₂ concentrations of about or greater than 23 mg l⁻¹. However, the combined AOP–BAC treatment showed significant reductions of 43%, 52%, and 59% relative to untreated raw water for DBPs, TOC, and UV₂₅₄, respectively.     

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide (UV/H₂O₂. The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined.

The DOC content and the UV-abs. of the water decreased substantially during treatment with UV/H₂O₂. The decreases were dependent on the time of irradiation (UV dose) as well as on the H₂O₂ dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and UV/H₂O₂-treated waters, respectively. No mutagenic activity was generated by the UV irradiation or the UV/H₂O₂ treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.