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1.
Ghauch A  Suptil J 《Chemosphere》2000,41(12):1835-1843
Atrazine, propazine and simazine were tested separately and in mixture by batch procedure in a laboratory-constructed apparatus. 3.75 l of a buffered s-triazines pesticide solution was treated at room temperature by 325-mesh zero-valent iron powder (ZVIP) (20 g/l). High performance liquid chromatography was used to separate by-products and study the decline in the pesticide’s concentrations. Results obtained show that the order of degradation was simazine, atrazine and then propazine. The half-lives (t1/2) of the s-triazines pesticides are, respectively, 7.4, 9.0 and 10.6 min when they are treated separately, and 9.8, 11.2 and 13.7 min when they are treated together under the same conditions. The final by-product obtained after 50 min of contact of simazine with ZVIP shows a shift to longer wavelength in its UV spectrum. A similar phenomenon is shown for atrazine and propazine. Identical primary by-products are produced and subsequently degraded to 4,6-(diamino)-s-triazine, which seems to be the major by-product of the reductive treatment process. Pathways for the degradation of the studied s-triazines by ZVIP are proposed.  相似文献   

2.
Atrazine, propazine and simazine were tested separately and in mixture by batch procedure in a laboratory-constructed apparatus. 3.75 l of a buffered s-triazines pesticide solution was treated at room temperature by 325-mesh zero-valent iron powder (ZVIP) (20 g/l). High performance liquid chromatography was used to separate by-products and study the decline in the pesticide’s concentrations. Results obtained show that the order of degradation was simazine, atrazine and then propazine. The half-lives (t1/2) of the s-triazines pesticides are, respectively, 7.4, 9.0 and 10.6 min when they are treated separately, and 9.8, 11.2 and 13.7 min when they are treated together under the same conditions. The final by-product obtained after 50 min of contact of simazine with ZVIP shows a shift to longer wavelength in its UV spectrum. A similar phenomenon is shown for atrazine and propazine. Identical primary by-products are produced and subsequently degraded to 4,6-(diamino)-s-triazine, which seems to be the major by-product of the reductive treatment process. Pathways for the degradation of the studied s-triazines by ZVIP are proposed.  相似文献   

3.
Ghauch A 《Chemosphere》2008,71(5):816-826
A study of the effect of zero-valent iron (ZVI) powder is carried out for the first time on the degradation of flutriafol ((RS)-2,4'-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, C(16)H(13)F(2)N(3)O), a bifluorinated soil and water persistent triazole pesticide using a laboratory scale device consisting of a 20 ml pyrex serum vials fixed to a Vortex agitator. Different amounts of ZVI powder (10-50 g l(-1)) at pH 6.6 and room temperature were investigated. Experiments showed an observed degradation rate k(obs) directly proportional to the surface of contact of flutriafol with ZVI. Flutriafol degradation reactions demonstrated first order kinetic with a half-live of about 10.8+/-0.5 min and 3.6+/-0.2 min when experiments were conducted at [ZVI]=10 g l(-1) into oxygenated and anoxic solutions, respectively. Three analytical techniques were employed to monitor flutriafol degradation and to understand solution and by-products behaviors: (1) A UV-Vis spectrophotometer; (2) a high performance liquid chromatography (HPLC) coupled with a photo diode array (PDA) and fluorescence detectors; (3) a similar HPLC coupled with a PDA and a mass spectrometer detectors equipped with an atmospheric pressure photoionization source. Results showed a complete disappearance of flutriafol after 20 min of contact with ZVI, the loss of fluorescence properties of the final by-products, the defluorination of the triazole pesticide via hydroxylation reaction and finally the hydrogenation of the triazole ring.  相似文献   

4.
Chu L  Wang J  Dong J  Liu H  Sun X 《Chemosphere》2012,86(4):409-414
In this study the treatment of coking wastewater was investigated by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Particular attention was paid to the effect of initial pH, dosage of H2O2 and to improvement in biodegradation. The results showed that higher COD and total phenol removal rates were achieved with a decrease in initial pH and an increase in H2O2 dosage. At an initial pH of less than 6.5 and H2O2 concentration of 0.3 M, COD removal reached 44-50% and approximately 95% of total phenol removal was achieved at a reaction time of 1 h. The oxygen uptake rate of the effluent measured at a reaction time of 1 h increased by approximately 65% compared to that of the raw coking wastewater. This indicated that biodegradation of the coking wastewater was significantly improved. Several organic compounds, including bifuran, quinoline, resorcinol and benzofuranol were removed completely as determined by GC-MS analysis. The advanced Fenton oxidation process is an effective pretreatment method for the removal of organic pollutants from coking wastewater. This process increases biodegradation, and may be combined with a classical biological process to achieve effluent of high quality.  相似文献   

5.
Heterogeneous photocatalytic degradation of three-selected herbicide derivatives: (1) picloram (4-Amino-3,5,6-trichloropyridine-2-carboxylic acid, (2) dicamba (2-Methoxy-3,6-dichlorobenzoic acid, and (3) floumeturon (N,N-Dimethyl-N-[3-(trifluoromethyl)phenyl]-urea) has been investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic technique and decrease in total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation of the herbicide was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO2, and in the presence of electron acceptors such as hydrogen peroxide (H2O2), potassium bromate (KBrO3), and ammonium persulphate (NH4)2S2O8 besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts in the case of dicamba (2) and floumeturon (3), whereas Hombikat UV100 was found to be better for the degradation of picloram (1). The herbicide picloram (1) was found to degrade faster as compared to dicamba (2) and floumeturon (3). The degradation products were analyzed by gas chromatography-mass spectrometry (GC/MS) technique, and plausible mechanisms for the formation of products have been proposed.  相似文献   

6.
Lee JY  Hozalski RM  Arnold WA 《Chemosphere》2007,66(11):2127-2135
Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l−1) conditions. The effect of short-term (25–105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l−1, the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l−1, the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.  相似文献   

7.
8.
Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe0) is mediated by the thin film of iron (hydr)oxides found on Fe0 under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl4) degradation by Fe0 was studied under the influence of various anions, ligands, and initial CCl4 concentrations ([P]o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl4 disappearance (kCCl4), and zero order for the appearance of dissolved Fe2+ (kFe2+). The rate of dechlorination exhibits saturation kinetics with respect to [P]o, suggesting that CCl4 is transformed at a limited number of reactive surface sites. Because oxidation of Fe0 by CCl4 is the major corrosion reaction in these systems, kFe2+ also approaches a limiting value at high CCl4 concentrations. The adsorption of borate strongly inhibited reduction of CCl4, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased kCCl4 (and kFe2+). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.  相似文献   

9.

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl?, SO42?, and PO43?, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P–O–C bonds, leading to the successive breakage of the three P–O–C bonds in TCPP to produce PO43?. In the second pathway, a C–Cl bond in part of the TCPP molecule was oxidized by SO4·? to carbonyl and carboxyl groups. The P–O–C bonds continued to react with ·OH to produce PO43?. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO4·?) and the reduction reaction (ZVI) did not completely degrade TCPP to CO2, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD50 and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (>?83.83%) were achieved in different types of soils.

  相似文献   

10.
超声波及其联用技术降解废水中的氯苯   总被引:7,自引:0,他引:7  
研究了在降解含氯苯废水的过程中,超声波分别与H2O2、O2、空气联用对氯苯降解效率的影响。结果表明,超声波分别与H2O2、O2、空气联用比单独使用超声波降解效率分别提高40、30、18个百分点。并且随H2O2用量的增加,降解效率明显升高。对于O2、空气,当气体流量小于0.3754mL/s时,降解效率随O2、空气流量的增大而明显升高。  相似文献   

11.
While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.  相似文献   

12.
Panax notoginseng (Burk.) F.H. Chen, a rare traditional Chinese medicinal herb, is a widely used phytomedicine used all over the world. In recent years, the arsenic contamination of the herb and its relative products becomes a serious problem due to elevated soil As concentration. This study aimed to evaluate the effects of different types and dosages of amendments on As stabilization in soil and its uptake by P. notoginseng. Results showed that comparing to control treatment, the As concentrations of P. notoginseng declined by 49–63%, 43–61% and 52–66% in 0.25% zero-valent iron (Fe(0)), 0.5% bauxite residue, and 1% zeolite treatment, respectively; whereas the biomasses were elevated by 62–116%, 45–152% and 114–265%, respectively. The As(III) proportions of P. notoginseng increased by 8%, 9%, and 8%, and the transfer factors of As from root to shoot increased by 37%, 42% and 84% in the optimal treatments of Fe(0), bauxite residue, and zeolite. For soil As, all the three amendments could transform the non-specifically adsorbed As fraction to hydrous oxides Fe/Al fractions (by Fe(0) and red mud) or specifically adsorbed As fraction (by zeolite), therefore reduced the bioavailability of soil As. With a comprehensive consideration of stabilization efficiency, plant growth, environmental influence, and cost, Fe(0) appeared to be the best amendment, and zeolite could also be a good choice. In conclusion, this study was of significance in developing As contamination control in P. notoginseng planting areas, and even other areas for medicinal herb growing.  相似文献   

13.
Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.  相似文献   

14.
Polycyclic aromatic hydrocarbons are very stable compounds and tend to bioaccumulate in the environment due to their high degree of conjugation and aromaticity. Hydrous pyrolysis is explored as a technique for the treatment of industrial water containing PAH, using anthracene as a model compound. The reactivity of anthracene under a range of temperatures and durations are studied in this paper. Aliquots of 1.0-10.0 mg of anthracene in a range of 1.0-5.0 mL of H2O are subjected to hydrous pyrolysis under varied conditions of temperature, reagents and duration. The conditions include oxidising systems comprising distilled water, hydrogen peroxide and Nafion-SiO2 solid catalyst in water; and reducing systems of formic acid and formic acid/Nafion-SiO2/Pd-C catalysts to assess a range of redox reaction conditions. Oxygen in air played a role in some of the reaction conditions. Pyrolysed products were identified and quantified by the use of Gas Chromatography-Mass Spectrometry (GC-MS). The major products were anthrone, anthraquinone, xanthone from oxidation; and multiple hydro-anthracene derivatives from reductive hydogenation. The nature of reaction conditions influenced the extent of anthracene degradation. The products formed are more reactive (less stable) as compared to anthracene the starting material and will therefore be less persistent in the environment.  相似文献   

15.
The effects of pesticides (a herbicide and a fungicide) on the microbial community structure and their activity were analyzed in soil from four alpine pasture grasslands in Slovakia. Specifically, the effects of the herbicide, Gesagard (prometryn active ingredient), and fungicide, Fundazol 50 WP (benomyl active ingredient), on the microbial respiration activity (CO2 production), the numbers of selective microbial physiological groups (CFU.g?1) and the structure (relative abundance) of soil microbial communities [(phospholipid fatty acid (PLFA)] were analyzed under controlled laboratory conditions. All treatments including the treatments with pesticides increased (statistically significantly) the production of CO2 in all fields during 21 days of incubation and posed a statistically insignificant negative influence on the numbers of the observed physiological groups of microorganisms. The significantly negative influence was evaluated only in the numbers of two physiological groups; spores of bacteria utilizing organic nitrogen and bacteria, and their spores utilizing inorganic nitrogen. A shift in the microbial composition was evident when the PLFA patterns of samples from different sites and treatments were compared by the Principal Component Analysis (PCA). According to the second component PCA 2 (15.95 %) the locations were grouped into two clusters. The first one involved the Donovaly and Dubakovo sites and the second one contained the Velka Fatra and Mala Fatra locations. The PLFA composition of the soils showed important changes after the treatment with pesticides according to PCA 1 (66.06 %). Other treatments had not had a significant effect on the soil microbial community with the exception of the population of fungi. The lower relative abundance (significant effect) of Gram-positive bacteria, actinomycetes and general group of bacteria were determined in samples treated by the herbicide Gesagard. The application of fungicide Fundazol decreased (statistically significantly) the relative abundance of actinomycetes and general group of bacteria and paradoxically increased the population of fungi.  相似文献   

16.
Spliid NH  Helweg A  Heinrichson K 《Chemosphere》2006,65(11):2223-2232
Filling and cleaning of pesticide sprayers presents a potential risk of pollution of soil and water. Three different solutions for handling sprayers have been suggested: Filling and cleaning in the field, filling and cleaning on hard surfaces with collection of the waste water, and filling and cleaning on a biobed, which is an excavation lined with clay and filled with a mixture of chopped straw, sphagnum and soil with turf on top, and with increased sorption capacity and microbial activity for degradation of the pesticides. In the present study the degradation and leaching of 21 pesticides (5 g of each) was followed in an established full-scale model biobed. Percolate was collected and analysed for pesticide residues, and the biobed material was sampled at three different depths and analysed by liquid chromatography double mass spectrometry (LC-MSMS). During the total study period of 563 days, no traces of 10 out of 21 applied pesticides were detected in the percolate (detection limits between 0.02 and 0.9 μg l−1) and three pesticides were only detected once and at concentrations below 2 μg l−1. During the first 198 days before second application, 14% of the applied herbicide bentazone was detected in the leachate with maximum and mean concentrations of 445 and 172 μg l−1, respectively. About 2% of the initial mecoprop and fluazifop dose was detected in the percolate, with mean concentrations of 23 μg l−1, while MCPA and dimethoate had mean concentrations of 3.5 and 4.7 μg l−1, respectively. Leachate concentrations for the remaining pesticides were generally below the detection limit (0.02–0.9 μg l−1, below 1% of applied). Sorption studies of five pesticides showed that compounds with a low Kd value appeared in the leachate. After 169 days, all pesticides in the biobed profile were degraded to a level below 50% of the calculated initial dose. Pesticides with Koc values above 100 were primarily found in the uppermost 10 cm and degraded slowest due to the low bioavailability. The 11 most degradable pesticides were all degraded such that less than 3% remained in the biobed after 169 days.

Following second pesticide application of the biobed, leachate was sampled 215 and 365 days after the treatment. This showed the same pesticides to be leached out and at concentrations comparable to those of the first treatment. The same pesticides as after the first treatment were retained in the biobed.  相似文献   


17.
Environmental Science and Pollution Research - A novel hybrid nanomaterial, nanoscale zero-valent iron (nZVI)-grafted imogolite nanotubes (Imo), was synthesized via a fast and straightforward...  相似文献   

18.
Feng W  Nansheng D  Helin H 《Chemosphere》2000,41(8):1233-1238
We have made a comparison of the UV-VIS spectra of three azo dyes, C. I. reactive red 2, orange II and C. I. reactive black 8, in aqueous solutions during treatment with iron powder reduction and photooxidation. From this, we propose their mechanisms for reduction photooxidation. GC/MS analyses of the degradation products of the dye C. I. reactive red 2 demonstrated some important steps producing hydrogenated azo structure, substituted benzene and substituted naphthalene.  相似文献   

19.
Budd R  O'geen A  Goh KS  Bondarenko S  Gan J 《Chemosphere》2011,83(11):1581-1587
Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time.In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 μm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived Kd values for the suspended solids were in the order of 104-105, substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 μm). Retention of suspended particles, especially the very large particles (>250 μm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT50 values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.  相似文献   

20.
Chlorinated aliphatic hydrocarbons are common groundwater contaminants. One possible remediation option is in-situ reductive dechlorination by zero-valent iron, either by direct injection or as reactive barriers. Chlorinated ethenes (tetrachloroethene: PCE; trichloroethene: TCE) have received extensive attention in this context. However, another common groundwater pollutant, 1,1,1-trichlorethane (TCA), has attracted much less attention. We studied TCA reduction by three types of granular zero-valent irons in a series of batch experiments using polluted groundwater, with and without added aquifer material. Two types of iron were able to reduce TCA completely with no daughter product concentration increases (1,1-dichloroethane: DCA; chloroethane: CA). One type of iron showed slower reduction, with intermediate rise of DCA and CA concentrations. When evaluating the formation of daughter products, the tests on the groundwater alone showed different results than the groundwater plus aquifer batches: DCA did not temporarily accumulate in the batches with added aquifer material, contrary to the batches without added aquifer material. 1,1-dichloroethene (DCE, also present in the groundwater as an abiotic degradation product of TCA) was also reduced slower in the batches without added aquifer material than in the batches with aquifer material. Redox potentials gradually decreased to low values in batches with aquifer material without iron, while the batches with groundwater alone maintained a constant higher redox potential. Either adsorption processes or microbiological activity in the samples could explain these phenomena. Polymerase Chain Reaction (PCR: a targeted gene probe technique) for chlorinated aliphatic compound (CAH)-degrading bacteria confirmed the presence of Dehalococcoides sp. (chloroethene-degraders) but was negative for Desulfobacterium autotrophicum (a known co-metabolic TCA degrader). DCA reduction was rate determining: first-order half-lives of 300-350 h were observed. TCA was fully removed within hours. CA is resistant to reduction by zero-valent iron but it is known to hydrolyze easily. Since CA did not accumulate in our batches, it may have disappeared by the latter mechanism or it may not have formed as a major daughter product.  相似文献   

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