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1.
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.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
Toor R  Mohseni M 《Chemosphere》2007,66(11):2087-2095
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.  相似文献   

5.
Follut F  Vel Leitner NK 《Chemosphere》2007,66(11):2114-2119
Aqueous 4-nitrophenol solutions containing TiO2 or Al2O3 nanoparticles were irradiated with electron beam. 4-nitrophenol was decomposed by the ionizing radiation process in the absence of the nanoparticles. The addition of TiO2 or Al2O3 (2 g l−1) before irradiation improved the removal of 4-nitrophenol, total organic carbon (TOC) but also nitrogen (TN). To identify the origin of the loss (catalysis or simply adsorption), TiO2 or Al2O3 nanoparticles were added after irradiation. Experiments show that the effect of the presence of TiO2 or Al2O3 during irradiation is just due to adsorption.  相似文献   

6.
UV/TiO2/H2O2, UV/TiO2 and UV/H2O2 were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l−1, UV/TiO2/H2O2 treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO2 and UV/H2O2. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r2 > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO2/H2O2 treatment. No pollutant removal was observed in the controls conducted with H2O2 or TiO2 only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO2/H2O2-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l−1. COD and Cl mass balances indicated UV, UV/H2O2, and UV/TiO2 treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.  相似文献   

7.
Zhu R  Sun L 《Chemosphere》2005,59(11):1583-1593
Methane fluxes were measured from three exposed tundra sites and four snowpack sites on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were −15.3 μg m−2 h−1 and −14.3 μg m−2 h−1, respectively. The fluxes from tundra site with fresh penguin dropping addition showed positive values with the average of 36.1 μg m−2 h−1, suggesting that the deposition of fresh droppings greatly enhanced CH4 emissions from the poor Antarctic tundra during penguin breeding periods. The summertime variation in CH4 flux was correlated with surface ground temperature and the precipitation. The correlation between the flux and PT0, which is the product of the precipitation and surface ground temperature, was quite strong. The diurnal cycle of CH4 flux from the tundra soils was not obtained due to local fluky weather conditions. The fluxes through four snowpack sites were also obtained by the vertical CH4 concentration gradient and their average fluxes were −46.5 μg m−2 h−1, −28.2 μg m−2 h−1, −46.4 μg m−2 h−1 and −17.9 μg m−2 h−1, respectively, indicating that tundra soils under snowpack also consume atmospheric CH4 in the maritime Antarctic; therefore these fluxes could constitute an important part of the annual CH4 budget for Antarctic tundra ecosystem.  相似文献   

8.
Walker JT  Geron CD  Vose JM  Swank WT 《Chemosphere》2002,49(10):1389-1398
In this paper, we present two years of seasonal nitric oxide (NO), ammonia (NH3), and nitrous oxide (N2O) trace gas fluxes measured in a recovering riparian zone with cattle excluded and adjacent riparian zone grazed by cattle. In the recovering riparian zone, average NO, NH3, and N2O fluxes were 5.8, 2.0, and 76.7 ng N m−2 s−1 (1.83, 0.63, and 24.19 kg N ha−1 y−1), respectively. Fluxes in the grazed riparian zone were larger, especially for NO and NH3, measuring 9.1, 4.3, and 77.6 ng N m−2 s−1 (2.87, 1.35, and 24.50 kg N ha−1 y−1) for NO, NH3, and N2O, respectively. On average, N2O accounted for greater than 85% of total trace gas flux in both the recovering and grazed riparian zones, though N2O fluxes were highly variable temporally. In the recovering riparian zone, variability in seasonal average fluxes was explained by variability in soil nitrogen (N) concentrations. Nitric oxide flux was positively correlated with soil ammonium (NH4+) concentration, while N2O flux was positively correlated with soil nitrate (NO3) concentration. Ammonia flux was positively correlated with the ratio of NH4+ to NO3. In the grazed riparian zone, average NH3 and N2O fluxes were not correlated with soil temperature, N concentrations, or moisture. This was likely due to high variability in soil microsite conditions related to cattle effects such as compaction and N input. Nitric oxide flux in the grazed riparian zone was positively correlated with soil temperature and NO3 concentration. Restoration appeared to significantly affect NO flux, which increased ≈600% during the first year following restoration and decreased during the second year to levels encountered at the onset of restoration. By comparing the ratio of total trace gas flux to soil N concentration, we show that the restored riparian zone is likely more efficient than the grazed riparian zone at diverting upper-soil N from the receiving stream to the atmosphere. This is likely due to the recovery of microbiological communities following changes in soil physical characteristics.  相似文献   

9.
Fenton''s type reaction and chemical pretreatment of PCBs   总被引:3,自引:0,他引:3  
This study evaluates the effects of Fenton's reagent (FR) on the rate and extent of the oxidative degradation of individual mono, di-, tri- and tetrachlorobiphenyls in the commercial mixture DELOR 103, equivalent to AROCLOR 1248. The oxidation effect of FR strongly increased with increasing the molar ratio of Fe2+/H2O2. The most effective oxidation of DELOR 103 (10 μg.ml−1) was achieved in a solution containing 1M H2O2 and 1 mM Fe2+. The FR elimination rate constants of PCB congeners decrease with increasing number of chlorine substituents in the biphenyl molecule and show a good correlation with the values of molecular weights of the PCB congeners and their 1-octanol/water partition coefficients.  相似文献   

10.
The temporal variability and bioaccumulation dynamics of C12–25 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-C12–25 (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-C15–17 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 Kow showed a parabolic pattern maximizing at n-C14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log Kow: 7.2–9.9), intermediate-size C14–18 n-alkanes and C15–20 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-C14–15 and isoprenoids.  相似文献   

11.
The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl4]2− and [PtCl6]2− in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients KD and KOC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl6]2− > [PtCl4]2− > carboplatin. Log KD-values were ranging from 2.5 to 4.3 , log KOC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l−1 Pt) and the effluent (2–150 μg l−1 Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log KD-values and log KOC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log KD – in the effluent of the MBR.  相似文献   


12.
Neamtu M  Siminiceanu I  Kettrup A 《Chemosphere》2000,40(12):1407-1410
The photodegradation of five representative nitromusk compounds in water has been performed in a stirred batch photoreactor with a UV low-pressure immersed mercury lamp, at constant temperature and different doses of hydrogen peroxide. The rate constants have been calculated on the basis of experimental data and a postulated first-order kinetic model. The rate constants, at 298 K and a dose of 1.1746 μmol l−1 H2O2 ranges from 0.3567 × 10−3 s−1 for musk tibetene, to 1.785 × 10−3 s−1 for musk ambrette.  相似文献   

13.
Long-chain alkylnitriles (CnH2n+1CN, where n=13, 15, 17) (LANs) and long-chain-trialkylamines (NCmH2m+1CnH2n+1CjH2j+1, where m,n = 1, 14, 16, 18 and j= 14, 16, 18) (TAMs) were identified for the first time in biota samples at concentrations ranging from 9–574 ng g−1 and from 157 to 825 (fresh wt. basis), respectively. In addition, the simultaneous occurrence in the aquatic environment of LANs and TAMs were also reported for the first time. The Kb values of both, LANs and TAMs varyied according to the different species but their were comparable to those found for PAHs.  相似文献   

14.
An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h−1 m−2 (30–60 ng h−1 per g dry plant––540–1080 ng h−1 per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (MS) and temperature coefficients were determined: βlimonene=0.108 K−1 and MS=14.57 μg h−1 m−2; βsabinene=0.095 K−1 and MS=5.39 μg h−1 m−2.

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.  相似文献   


15.
Haggi E  Bertolotti S  García NA 《Chemosphere》2004,55(11):1501-1507
The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O2√−) and singlet molecular oxygen (O2(1Δg)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O2(1Δg) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O2√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O2√−, since O2(1Δg) is quenched in an exclusive physical fashion by the ArOH. The production of O2√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.  相似文献   

16.
Perfluorooctanesulfonyl fluoride (POSF, C8F17SO2F) related-materials have been used as surfactants, paper and packaging treatments, and surface (e.g., carpet, textile, upholstery) protectants. A metabolite, perfluorooctanesulfonate (PFOS, C8F17SO3), has been identified in the serum and liver of non-occupationally exposed humans and wildlife. Because of its persistence, an important question was whether elderly humans might have higher PFOS concentrations. From a prospective study designed to examine cognitive function in the Seattle (WA) metropolitan area, blood samples were collected from 238 dementia-free subjects (ages 65–96). High-pressure liquid chromatography-electrospray tandem mass spectrometry determined seven fluorochemicals: PFOS; N-ethyl perfluorooctanesulfonamidoacetate; N-methyl perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamidoacetate; perfluorooctanesulfonamide; perfluorooctanoate; and perfluorohexanesulfonate. Serum PFOS concentrations ranged from less than the lower limit of quantitation (3.4 ppb) to 175.0 ppb (geometric mean 31.0 ppb; 95% CI 28.8–33.4). An estimate of the 95% tolerance limit was 84.1 ppb (upper 95% confidence limit 104.0 ppb). Serum PFOS concentrations were slightly lower among the most elderly. There were no significant differences by sex or years residence in Seattle. The distributions of the other fluorochemicals were approximately an order of magnitude lower. Similar to other reported findings of younger adults, the geometric mean serum PFOS concentration in non-occupational adult populations likely approximates 30–40 ppb with 95% of the population’s serum PFOS concentrations below 100 ppb.  相似文献   

17.
The influence of intact (FLT) and photomodified (phFLT) fluoranthene (0.05, 0.5 and 5 μmol l−1) and herbicide Basagran (5, 20, 35 and 50 nmol l−1) on the germination, growth of seedlings and photosynthetic processes in pea plants (Pisum sativum L., cv. Garde) was investigated. The germination was significantly inhibited already by the lowest concentration (0.05 μmol l−1) of FLT and phFLT, while Basagran caused inhibition only in higher concentrations (35 and 50 nmol l−1). The growth of roots was significantly inhibited by higher concentration 5 μmol l−1 of both FLT and phFLT and the shoot of seedlings was significantly influenced only by photomodified form. The length of root and shoot was inhibited already by concentration 5 nmol l−1 of Basagran. Organic compounds applied on chloroplasts suspension influenced primary photochemical processes of photosynthesis. In chlorophyll fluorescence parameters, the significant increase of F0 values and the decrease of FV/FM and ΦII values by application of FLT (0.5 and 5 μmol l−1) and phFLT (0.05, 0.5 and 5 μmol l−1) was recorded. The maximum capacity of PSII (FV/FM) was influenced by the highest (50 nmol l−1) and the effective quantum yield of PSII (ΦII) already by the lowest (5 nmol l−1) concentration of Basagran. Hill reaction activity decreased and was significantly inhibited by higher concentration (0.5 and 5 μmol l−1) of FLT and phFLT and already by the lowest concentration (5 nmol l−1) of Basagran.  相似文献   

18.
The combined electrochemical oxidation-solar-light/immobilized TiO2 film process was conducted to degrade an azo dye, Reactive Black 5 (RB5). The toxicity was also monitored by the Vibrio fischeri light inhibition test. The electrochemical oxidation rapidly decolorized RB5 (55, 110 μM) with a supporting electrolyte of 2 g l−1 NaCl at current density 277 A m−2 and pH 4. However, TOC mineralization and A310 removal were low. Additionally, the treated solution showed high biotoxicity. RB5 at 110 μM significantly retarded the de-colorization efficiency by using the solar-light/immobilized TiO2 film process. The combined electrochemical oxidation-solar-light/immobilized TiO2 process effectively increased the removal of color, A310, and TOC. The toxicity was also significantly reduced after 3 h of solar irradiation. The results indicated that the low-cost combined process is a potential technique for rapid treatment of RB5.  相似文献   

19.
Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO2 immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO2 concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO2 concentration of the coating solution: 10%; Fe(II): 7.0 mg l−1; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l−1 As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l−1) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO2 can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO2 immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.  相似文献   

20.
The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope (202Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF6) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l−1 in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m−2 yr−1, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m−2 h−1, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.  相似文献   

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