Ozone oxidation and aerobic biodegradation with spent mushroom compost for detoxification and benzo(a)pyrene removal from contaminated soil

The combination of ozonation and spent mushroom compost (SMC)-mediated aerobic biological treatment was investigated in the removal of benzo(a)pyrene from contaminated soil. The performances of the process alone and combined were evaluated in terms of benzo(a)pyrene removal efficiency, mineralization efficiency (as total organic carbon removal), and soil residual toxicity (phytotoxicity to Lepidium Sativum and toxicity to Vibrio fischeri). In spite of the removal efficiency (35%) obtained by SMC-mediated biological process as a stand-alone treatment, the combined process showed a benzo(a)pyrene concentration reduction higher than 75%; the best removal (82%) was observed after 10 min pre-ozonation treatment. In particular, ozonation improved the biodegradability of the contaminant, as confirmed by the increase of CO(2) production (close to 70% compared to the control), mineralization (greater than 60%) and bacterial density (which increased by two orders of magnitude). Moreover, according to phytotoxicity tests on L. Sativum, the aerobic biological process of pre-ozonated soil decreased toxicity. According to the results achieved in the present study, ozonation pre-treatment showed an high potential to overcome the limitation of bioremediation of recalcitrant compound, but it should be carefully operated in order to maximize PAH removal efficiency as well as to minimize soil residual toxicity which can result from the formation of the oxidation intermediates.     

臭氧处理剩余污泥的减量化实验研究

采用质子交换聚合物膜电解法（PEM）产生臭氧,单独对剩余污泥进行氧化破解实验,结果表明,随着臭氧化反应时间的增加,污泥微生物细胞裂解,胞内物质进入到污泥溶液中,污泥固体物质减少,使得TS和VTS均显著下降,处理40 min后,其去除率分别达到57.33%和72.76%;SCOD前30 min呈线性增长,通入臭氧60 min后,由处理前的3 501.24mg/L上升到6 298.32 mg/L,增长率达79.88%;SV30及滤饼含水率均呈下降趋势,表明剩余污泥的沉淀性能及脱水性能得到明显改善。实验结果表明,直接利用臭氧对剩余污泥进行处理,可获得良好的减量化效果。     

FIA/MS analysis of temporally ozonated benzo[a]pyrene and pyrene and their reaction products: inhibition of gap junction-mediated intercellular communication

In this study, the polycyclic aromatic hydrocarbons, benzo[a]pyrene (BaP) and pyrene, were subjected to temporal ozonation. The products from ozonation of 5 mg l(-1) BaP and 5 mg l(-1) pyrene, for varying time intervals (0, 1, 2, 3, 4, 5, 6, 8, 10, 20, and 30 min) were tested for their effects on gap junction-mediated intercellular communication (GJIC) in Clone 9 rat liver cells. Additionally, the ozonation products were also analyzed by flow injection analysis/mass spectrometry (FIA/MS) and the results were compared with the toxicity observed in the GJIC assay. Treatment of the Clone 9 cells with 5 mg l(-1) of ozonated BaP products resulted in a decrease in GJIC that was inversely proportional to the length of ozonation. The products from 1 min of ozonation resulted in a 92% decrease in the rate of GJIC, but with >5 min ozonation, the products did not suppress GJIC. In contrast, pyrene (0.5 mg l(-1)) required >10 min of ozonation to alleviate its effects on GJIC. FIA/MS, using atmospheric pressure chemical ionization (APCI), demonstrated products with higher molecular weights (MW) than their corresponding parent compounds, BaP (MW 252) and pyrene (MW 202). Ozonation of pyrene formed significantly fewer products than BaP. More importantly, pyrene ozonation products were constant from 1 to 10 min, while BaP ozonation products seemed to vary between time intervals. With the longer ozonation times (20 and 30 min), BaP and pyrene formed similar products (m/z peaks 157, 111, and 96). The suppression of GJIC by ozonated products seemed to correlate with oxidation of the aromatic ring framework. Further oxidation (longer ozonation times) to lower MW products correlated with restoration of normal GJIC.     

原位臭氧氧化对活性污泥系统硝化和反硝化作用的影响研究

将厌氧序批式间歇反应器(ASBR)和序批式间歇反应器(SBR)串联组成污泥减量新工艺,着重探讨了对SBR段进行原位臭氧投加时,臭氧氧化作用对系统硝化和反硝化能力的影响,并以不投加作为对照。结果表明,将臭氧原位投加到ASBR—SBR组合工艺的SBR段,臭氧投加量为0.027g(以每克MLSS计),每隔3个周期再次投加、连续运行40d,试验组SBR段臭氧投加当期出水COD去除率为86%,比对照组下降了9百分点,但臭氧氧化细胞内大量有机物进入混合液中,为反硝化作用提供了外加碳源,对污泥反硝化能力的提高起到了一定的促进作用;试验组部分硝化细菌由于臭氧的强氧化作用而失去活性,但是随着剩余污泥量的减少,系统的污泥龄延长,有利于硝化细菌的生长,使得系统的硝化能力基本未受影响;试验组臭氧投加当期SBR段出水NO2--N平均浓度比对照组的高18.9%,但经过3个周期的运行后,其SBR段出水NO2--N平均质量浓度降低至7.57mg/L,基本与对照组持平;试验组臭氧投加当期SBR段出水NO3--N的平均浓度高于对照组,但经过3个周期的运行后,试验组出水NO3--N平均浓度低于对照组;试验组臭氧投加当期SBR段出水TN和对照组的出水TN平均去除率分别为65%和75%,但试验组再经过3个周期的运行后,出水TN平均去除率可以达到72%。可见,原位投加臭氧并未对SBR段的硝化和反硝化能力产生明显的影响。     

Sequential UV-biological degradation of polycyclic aromatic hydrocarbons in two-phases partitioning bioreactors

A method based on UV-irradiation in organic solvent followed by transfer of the remaining pollutants into silicone oil for subsequent biodegradation in a biphasic system inoculated with a phenanthrene degrading Pseudomonas sp. was tested for the treatment of various mixtures of PAHs. Acetone was first selected as the most suitable solvent compared to methanol, acetonitrile and silicone oil for the removal of pyrene and phenanthrene. The sequential treatment was then applied to the treatment of a mixture of fluorene, phenanthrene, anthracene, fluoranthrene, pyrene, benzo(a)anthracene and benzo(a)pyrene in acetone. These compounds were photodegraded in the following order of initial removal rates (mg l(-1) d(-1)): benzo(a)pyrene (7.8) > anthracene (5.0) > benzo(a)anthracene (2.5) > fluoranthrene (1.8) > pyrene (1.5) > phenanthrene (1.2) > fluorene (0.2). UV-treatment allowed complete removal of, anthracene, benzo(a)anthracene and benzo(a)pyrene and removals of 63% of pyrene and 37% of fluorene after 434 h or irradiation. The subsequent biological treatment removed the remaining phenanthrene and fluorene by 100% and 90%, respectively, after 790 h of cultivation. Although less efficient due to the presence of interfering compounds, the UV-biological treatment of a soil extract allowed a 63% removal of the seven PAHs named above. Microbial growth did not occur when the pollutants were directly supplied to the microorganism showing that biphasic systems reduced the toxicity effects cause by mixtures of PAHs at high concentrations. This study demonstrates the potential of selective UV treatment of high molecular weight PAHs followed by biological treatment of the low molecular weight species in biphasic systems.     

污泥减量过程中臭氧氧化对硝化和反硝化影响的试验研究

采用AO工艺,考察了在污泥减量过程中臭氧(O3)氧化对生物系统硝化和反硝化能力的影响.结果表明,在每克SS中O3投量为0.05 g时,氧化后污泥中的CODcr由37.5 mg/L增至700mg/L,TN由4.86 mg/L增至36.6 mg/L,NH4 -N由0.353mg/L增至7.49 mg/L,NO3--N由2.19 mg/L增至5.15 mg/L.虽然氧化系统出水NH4 -N浓度略高于对照系统,但氧化系统NH4 -N的去除率大于98%,硝化能力基本没有受到O3氧化的影响.O3氧化污泥后增加的有机物作为附加的碳源循环至缺氧段,提高了反硝化的效果,当污泥氧化比例分别为10%、20%、30%时,进入缺氧段的CODCr/TN分别平均增至11.21、11.56、11.88,氧化系统的反硝化效果也随之分别提高5%、25%、37%.     

Ozonation of aniline promoted by activated carbon

The removal of aniline from aqueous solutions by simultaneous use of ozone and activated carbon was investigated at different solution pH. For comparative purposes, single ozonation and adsorption on activated carbon were carried out in the same experimental set-up. In order to evaluate the role of the activated carbon surface chemistry during ozonation, a commercial activated carbon, Norit GAC 1240 PLUS, was submitted to oxidation in the liquid phase with HNO(3). The texture and surface chemistry of the activated carbon samples were characterized. During ozonation, complete conversion of aniline was achieved after approximately 20 min, regardless of the presence of activated carbon. In all cases, several by-products were formed during ozonation. Nitrobenzene, o- and p-aminophenol were the primary aromatic oxidation by-products identified. In terms of TOC removal, best results were achieved by the simultaneous use of ozone and activated carbon. Though there is a strong contribution of adsorption, a considerable synergetic effect between ozone and activated carbon is observed. In general, activated carbon promotes the reaction of ozonation enhancing the efficiency of this treatment process. The basic activated carbon presented greater activity in this process leading to higher mineralization rates.     

Treatment of distillery spent-wash by ozonation and biodegradation: significance of pH reduction and inorganic carbon removal before ozonation.

This study is aimed at exploring strategies for mineralization of refractory compounds in distillery effluent by anaerobic biodegradation/ozonation/aerobic biodegradation. Treatment of distillery spent-wash used in this research by anaerobic-aerobic biodegradation resulted in overall COD removal of 70.8%. Ozonation of the anaerobically treated distillery spent-wash was carried out as-is (phase I experiments) and after pH reduction and removal of inorganic carbon (phase II experiments). Introduction of the ozonation step resulted in an increase in overall chemical oxygen demand (COD) removal, with the highest COD removals of greater than 95% obtained when an ozone dose of approximately 5.3 mg ozone absorbed/mg initial total organic carbon was used. The COD removal during phase II experiments was slightly superior compared with phase I experiments at similar ozone doses. Moreover, efficiency of ozone absorption from the gas phase into distillery spent-wash aliquots was considerably enhanced during phase II experiments.     

造纸中段废水的混凝-臭氧氧化深度处理研究

就混凝-臭氧氧化组合工艺对造纸中段废水生物处理出水的净化效果进行了研究.结果表明,Ca(OH)2对废水色度、TOC、COD和254 nm的紫外吸收值(UV254)的去除效果均优于聚合氯化铝/聚丙烯酰胺(PAC/PAM);Ca(OH)2-O3组合工艺的处理效果也优于PAC/PAM-O3工艺.当Ca(OH)2投加量为1 g/L、臭氧投加量为50 mg/L时,废水色度降低至10倍以下,COD小于150 mg/L.经Ca(OH)2混凝处理后,相对分子量在0.5～1.0 ku和10.0 ku以上的有机物显著减少;进一步臭氧氧化处理后,除0.5 ～1.0 ku范围的有机物大幅度增加外,其余分子量有机物显著减少.由于对色度贡献很大的大分子量物质的去除,废水的色度显著下降直至无色.     

Enhancement of chemical-oxygen demand and color removal of distillery spent-wash by ozonation.

Distillery spent-wash has very high organic content (75,000 to 125,000 mg/L chemical-oxygen demand [COD]), color, and contains difficult-to-biodegrade organic compounds. For example, anaerobic treatment of the distillery spent-wash used in this study resulted in 60% COD reduction and low color removal. Subsequent aerobic treatment of the anaerobic effluent resulted in enhancement of COD removal to 66%. In this paper, the effect of ozonation on various properties of the anaerobically treated distillery effluent, including the effect on its subsequent aerobic biodegradation, was investigated. Ozonation of the anaerobically treated distillery effluent at various ozone doses resulted in the reduction of total-organic carbon (TOC), COD, COD/TOC ratio, absorbance, color, and increase in the biochemical-oxygen demand (BOD)/COD ratio of the effluent. Further, ozonation of the anaerobically treated distillery effluent at an ozone dose of 2.08 mg/mg initial TOC and subsequent aerobic biodegradation resulted in 87.4% COD removal, as compared to 66% removal when ozonation was not used.     

Efficacy of in-situ for the remediation of PAH contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are of environmental concern because many PAHs are either carcinogens or potential carcinogens. Petroleum products are a major source of PAHs. The occurrence of PAH contamination is widespread and novel treatment technologies for the remediation of contaminated soils are necessary.Ozone has been found to be extremely useful for the degradation of PAHs in soils. For these compounds, the reaction with molecular ozone appears to be the more important degradation pathway. Greater than 95% removal of phenanthrene was achieved with an ozonation time of 2.3 h at an ozone flux of 250 mg h⁻¹. After 4.0 h of treatment at an ozone flux of 600 mg h⁻¹, 91 % of the pyrene was removed. We have also found that the more hydrophobic PAHs (e.g. chrysene) react more slowly than would be expected on the basis of their reactivity with ozone, suggesting that partitioning of the contaminant into soil organic matter may reduce the reactivity of the compound. Even so, after 4 h of exposure to ozone, the chrysene concentration in a contaminated Metea soil was reduced from 100 to 50 mg kg⁻¹ .Ozone has been found to be readily transported through columns packed with a number of geological materials, including Ottawa sand, Metea soil, Borden aquifer material and Wurtsmith aquifer material. All of these geological materials exerted a limited (finite) ozone demand, i.e. the rate of ozone degradation in soil columns is very slow after the ozone demand is met. Moisture content was found to increase the ozone demand, most likely owing to the dissolution of gaseous ozone into the pore water. As once the initial ozone demand is met, little degradation of ozone is observed, it should be possible to achieve ozone penetration to a considerable distance away from the injection well, suggesting that in-situ ozonation is a feasible means of treating uncontaminated unsaturated soils. This is substantiated by two field studies where in-situ ozonation was apparently successful at remediating the sites.     

A two-stage process using electrokinetic remediation and electrochemical degradation for treating benzo[a]pyrene spiked kaolin

An innovative process that combines soil electrokinetic remediation and liquid electrochemical oxidation for the degradation of organic compounds present in a polluted soil was developed and evaluated by using benzo[a]pyrene spiked kaolin. In order to increase benzo[a]pyrene solubility during electrokinetic treatment, the addition of a co-solvent or surfactant, such as ethanol or Brij 35, as flushing solution was tested. The research carried out demonstrated the influence of the desorption agent employed on benzo[a]pyrene remediation from the kaolin matrix. Thus, if the flushing solution was ethanol at 40%, there was no presence of contaminant in either chamber. On the contrary, when a solution of surfactant Brij 35 was used, benzo[a]pyrene was transported towards the cathode chamber, where it was collected. Moreover, the extent of this recovery depends on the pH profile on the soil. When no pH control was used, around 17% of initial contaminant was detected in the cathode chamber; however, when pH control was applied, the recovery of benzo[a]pyrene could be higher than 76%, when the pH control in the anode chamber was set at 7.0.In order to obtain the total degradation of mobilised benzo[a]pyrene from the contaminated soil, the liquid collected by electrokinetic remediation was oxidised by electrochemical treatment. This oxidation was accomplished via an electrochemical cell with a working volume of 0.4 L, and graphite as electrode material. The benzo[a]pyrene was almost totally degraded in 1 d, reaching a degradation of about 73% in 16 h.     

The effect of nitrogen dioxide on the photochemical and nonphotochemical degradation of pyrene and benzo[a]pyrene adsorbed on coal fly ash

Nitration by NO₂ of pyrene or benzo[a]pyrene adsorbed from the vapor phase onto six coal ashes, alumina, and silica substrates is not observed if the NO₂ is thoroughly purged of nitric acid. Also, the photochemical transformation of pyrene or benzo[a]pyrene adsorbed on these substrates is not detectably influenced by the presence of nitric acid-free NO₂. Photochemical production of nitro derivatives of adsorbed polycyclic aromatic hydrocarbons in the presence of NO₂ does not appear to be a significant process unless appreciable concentrations of nitric acid, or perhaps strong oxidants such as ozone, also are present.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.     

Effects of alfalfa and organic fertilizer on benzo[a]pyrene dissipation in an aged contaminated soil

BACKGROUND: A climate-controlled pot experiment was conducted to investigate the effects of planting alfalfa and applying organic fertilizer on the dissipation of benzo[a]pyrene from an aged contaminated agricultural soil. RESULTS: Short-term planting of alfalfa inhibited the dissipation of benzo[a]pyrene from the soil by 8.9%, and organic fertilizer enhanced benzo[a]pyrene removal from the soil by 11.6% compared with the unplanted and unfertilized treatments, respectively. No significant interaction was observed between alfalfa and organic fertilizer on benzo[a]pyrene dissipation. Sterilization completely inhibited the removal of benzo[a]pyrene from the soil indicating that its degradation by indigenous microorganisms may have been the main mechanism of dissipation. Furthermore, significant positive relationships were observed between benzo[a]pyrene removal and the contents of soil ammonium nitrogen, nitrate nitrogen, and total mineral nitrogen at the end of the experiment, suggesting that competition between plants and microorganisms for nitrogen may have inhibited benzo[a]pyrene dissipation in the rhizosphere of alfalfa and the addition of organic fertilizer may facilitate microbial degradation of benzo[a]pyrene in the soil.     

Treatment of groundwater contaminated with gasoline components by an ozone/UV process

In this paper, the treatment of real groundwater samples contaminated with gasoline components, such as benzene, toluene, ethylbenzene, and xylene (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and other gasoline constituents in terms of total petroleum hydrocarbons as gasoline (TPHg) by an ozone/UV process was investigated. The treatment was conducted in a semi-batch reactor under different experimental conditions by varying ozone gas dosage and incident UV light intensity. The groundwater samples contained BTEX compounds, MTBE, TBA, and TPHg in the ranges of 5-10000, 3000-5500, 80-1400, and 2400-20000mugl(-1), respectively. The ozone/UV process was very effective compared to ozonation in the removal of the gasoline components from the groundwater samples. For the various gasoline constituents, more than 99% removal efficiency was achieved for the ozone/UV process and the removal efficiency for ozonation was as low as 27%. The net ozone consumed per mol of organic carbon (from BTEX, MTBE, and TBA) oxidized varied in the range of 5-60 for different types of groundwater samples treated by the ozone/UV process. In ozonation experiments, it was observed that the presence of sufficient amount of iron in groundwater samples improved the removal of BTEX, MTBE, TBA, and TPHg.     

不同工艺再生水补给对景观湖水质变化的影响

再生水回用于景观水体过程中,为了比较不同再生水工艺对景观水体富营养化的影响,以"二级出水+BAF+O3+GFH"和"二级出水+O3"作为再生水处理工艺,以岸滤(bank filtration,BF)作为水质维持工艺,进行再生水景观水体水质保障技术研究。结果表明,"二级出水+O3"出水流量较大,水力流动快,每天运行24 h,平均出水流量25.5 m3/d,氮磷含量偏高;"二级出水+BAF+O3+GFH"出水的氮磷指标控制在较低水平,GFH出水流量8～14 m3/d,水力流动较缓,湖中出现蓝藻。2套系统中BF对NH4+-N的去除率分别为30.5%和20.8%。"二级出水+O3+BF"系统中人工湖进水TN平均浓度24.309 mg/L,TP平均浓度0.583 mg/L,N/P=41,适宜水网藻生长,对湖中N(主要是NH4+-N)、P有较强的去除能力;"二级出水+BAF+O3+GFH+BF"系统中人工湖进水TP<0.05 mg/L,适宜蓝藻生长。     

微气泡曝气O3／H2O2处理RO浓水的效能及影响因素

采用O3／H2O2高级氧化工艺处理炼油厂反渗透（RO）浓水，用溶气泵加压溶气并产生微气泡强化传质，确定装置运行条件，考察气体中臭氧浓度、O3／H2O2初始摩尔比、pH和温度对O3／H2O2处理RO浓水效果的影响，并对RO浓水处理效能进行研究。结果表明，随着气体中臭氧浓度的增加，COD的去除率基本呈线性增加；加入适当量H，0，能提高臭氧氧化RO浓水的效果，O3／H2O2初始摩尔比在0～0．8范围内，COD的去除率先增加后下降，O3／H2O2初始摩尔比为O．5时COD去除率最大；pH从6．84增加到9．01，COD去除率逐渐增大，pH为10．03时COD去除率反而降低；在14～28℃范围内，温度低时，升高温度COD去除率增加较大，温度较高时，升高温度对COD去除率的影响较小。为考察该工艺的稳定性，在H：0：／0，初始摩尔比为O．5、溶液pH为8～9、臭氧浓度为80～100mg／L、温度为10-28℃条件下，对COD为90～140mg／L的RO浓水氧化处理4～10h，出水COD维持在39．9～49．9mg／L，达到《城镇污水处理厂污染物排放标准（GB18918—2002）》中的一级A标准；去除1gCOD消耗031．4～3．3g，消耗0，与H，02的总氧量为2．2～4．4g。     

原位臭氧氧化污泥减量工艺的运行效能

采用ASBR/SBR原位臭氧污泥减量工艺,重点研究了原位臭氧氧化对SBR段污泥产率和出水水质的影响。两个相同的ASBR/SBR组合工艺同时运行,每隔3个周期向臭氧投加组SBR的曝气阶段原位间歇投加臭氧,臭氧投加量为0.027 g O3/g MLSS,连续运行40 d;对照组不投加臭氧作为对比。结果表明,原位臭氧氧化实现污泥减量约43.9%,臭氧投加组SBR段平均污泥产率系数为0.1447 g SS/g SCOD,而对照组为0.2580 g SS/g SCOD,投加组没有惰性污泥的累积,并且污泥沉淀性能得到改善。原位臭氧氧化对出水水质影响不大,投加组与对照组相比,臭氧投加3周期后的出水COD、NH4+-N、TN和TP平均值分别为47.8、0.76、14.1和6.4 mg/L,去除率分别下降了4%、2%、3%和7.7%,其中COD、NH4+-N和TN均能达到《城镇污水处理厂污染物排放标准》(GB18918-2002)一级A标准。     

Combination of ozonation with conventional aerobic oxidation for distillery wastewater treatment

Laboratory-scale experiments were conducted in order to investigate the effect of ozone as pre-aerobic treatment and post-aerobic treatment for the treatment of the distillery wastewater. The degradation of the pollutants present in distillery spent wash was carried out by ozonation, aerobic biological degradation processes alone and by using the combinations of these two processes to investigate the synergism between the two modes of wastewater treatment and with the aim of reducing the overall treatment costs. Pollutant removal efficiency was followed by means of global parameters directly related to the concentration of organic compounds in those effluents: chemical oxygen demand (COD) and the color removal efficiency in terms of absorbance of the sample at 254 nm. Ozone was found to be effective in bringing down the COD (up to 27%) during the pretreatment step itself. In the combined process, pretreatment of the effluent led to enhanced rates of subsequent biological oxidation step, almost 2.5 times increase in the initial oxidation rate has been observed. Post-aerobic treatment with ozone led to further removal of COD along with the complete discoloration of the effluent. The integrated process (ozone-aerobic oxidation-ozone) achieved approximately 79% COD reduction along with discoloration of the effluent sample as compared to 34.9% COD reduction for non-ozonated sample, over a similar treatment period.