O3/H2O2降解阿特拉津影响因素研究

采用O3/H2O2氧化去除水中内分泌干扰物阿特拉津,考察了反应条件及水质对去除的影响,并对反应机制进行了初步探讨。阿特拉津初始浓度2 mg/L,投量为7.5 mg/L的O₃单独氧化去除率为27.2%;相同O₃投量下,控制H₂O₂/O₃摩尔比为0.75,5 min阿特拉津的去除率最高可达96.5%;pH 值为7.5～8.5,温度在25～40℃的范围内,都维持了较高的去除率,表明H₂O₂/O₃体系对阿特拉津的去除效果良好,降解速度快,反应条件温和。0.5 mg/L的腐殖酸,对阿特拉津的去除影响不大,腐殖酸浓度为1、2和5 mg/L时,平均去除率分别为63.4%、50.7%和30.2%;碳酸氢钠的浓度为50和200 mg/L时,去除率分别为88.1%和73.8%,说明水质对阿特拉津的去除影响较大。叔丁醇的浓度为5和20 mg/L时,阿特拉津的去除率分别降低到44.7%和27.5%,去除率随自由基抑制剂叔丁醇增加而降低,说明H₂O₂/O₃降解阿特拉津主要为该体系产生的羟基自由基的贡献。     

O3/H2O2降解阿特拉津影响因素研究

采用O3/H2O2氧化去除水中内分泌干扰物阿特拉津,考察了反应条件及水质对去除的影响,并对反应机制进行了初步探讨.阿特拉津初始浓度2 mg/L,投量为7.5 mg/L的O3单独氧化去除率为27.2%;相同O3投量下,控制H2O2/O3摩尔比为0.75,5 min阿特拉津的去除率最高可达96.5%;pH值为7.5～8.5,温度在25～40℃的范围内,都维持了较高的去除率,表明H2O2/O3体系对阿特拉津的去除效果良好,降解速度快,反应条件温和.0.5 mg/L的腐殖酸,对阿特拉津的去除影响不大,腐殖酸浓度为1、2和5 mg/L时,平均去除率分别为63.4%、50.7%和30.2%;碳酸氢钠的浓度为50和200 mg/L时,去除率分别为88.1%和73.8%,说明水质对阿特拉津的去除影响较大.叔丁醇的浓度为5和20 mg/L时,阿特拉津的去除率分别降低到44.7%和27.5%,去除率随自由基抑制剂叔丁醇增加而降低,说明H2O2/O3降解阿特拉津主要为该体系产生的羟基自由基的贡献.     

羟基氧化铁催化臭氧氧化去除水中阿特拉津

以实验室制备的羟基氧化铁(FeOOH)为催化剂,研究了其催化臭氧氧化去除水中痕量阿特拉津的效能,并对影响催化效果因素及降解机理进行了探讨。在本实验条件下,反应8 min时催化氧化阿特拉津的去除率比单独臭氧氧化高出63.2%,而FeOOH对阿特拉津的吸附量很小,结果表明,FeOOH对臭氧氧化水中的痕量阿特拉津具有明显的催化活性。探讨了催化剂投量、pH、阿特拉津初始浓度和重碳酸盐碱度对催化氧化阿特拉津的影响。催化剂最佳投量为150 mg/L,去除率随pH和阿特拉津初始浓度的增加而升高,重碳酸盐浓度为200 mg/L时催化作用受到明显抑制。通过研究叔丁醇对催化反应的影响间接推断了催化反应的机理,叔丁醇作为羟基自由基抑制剂有效地抑制了水中羟基自由基的生成和它对阿特拉津的氧化反应,间接证明这种催化作用遵循羟基自由基的反应机理。     

水中腐殖酸可见光降解阿特拉津的动力学研究

探讨了天然水体中存在的腐殖酸(HA)可见光降解水中阿特拉津的动力学特征和影响因素。结果表明,pH对HA可见光降解阿特拉津具有明显影响,水中HA质量浓度为5.0mg/L时,pH为3、5、7、9的条件下,受可见光照6.00h后阿特拉津(初始质量浓度5mg/L)的去除率分别为75.5%、77.3%、91.7%、84.9%,中性条件下阿特拉津可见光降解效果最佳;当HA质量浓度分别为1.5、3.0、5.0、10.0mg/L时,HA对水中阿特拉津的可见光降解均表现为促进作用,且降解过程符合一级反应动力学方程,其一级反应动力学常数分别为0.337 0、0.361 4、0.445 4、0.314 6h-1,HA为5.0mg/L时阿特拉津的可见光降解效果最佳。实际应用中,可以通过优化HA与阿特拉津的浓度比值,发挥HA促进阿特拉津可见光降解的最佳效能。     

寒地黑土中阿特拉津降解菌的筛选及降解特性

从长期施用阿特拉津的寒地黑土耕层(0～10 cm)取样。利用富集培养的方法,筛选到2株阿特拉津降解菌,编号Z₉和Z₄₂。Z₉以阿特拉津为惟一碳氮源生长,Z₄₂以阿特拉津为惟一氮源生长,15 d对阿特拉津的降解率分别为77.7%和65.6%。对其初步鉴定并对降解特性进行研究,结果表明,细菌Z9为微杆菌属（Microbacterium sp.）,细菌Z₄₂为节杆菌属(Arthrobacter sp.)。在室内进行降解条件优化实验,得出2株降解菌对100 mg/L阿特拉津的最佳降解条件为：温度30℃,Z₉ pH值为7,Z₄₂ pH值为8。     

基于绿色合成法的纳米铁/活性炭复合材料降解阿特拉津的动力学

为了综合处理水中的阿特拉津,以绿茶萃取液为还原剂,以活性炭为载体,采用液相还原法绿色合成了纳米铁/活性炭复合材料,研究了活性炭投放量、阿特拉津的初始浓度、溶液初始pH值及反应时间对阿特拉津去除率的影响,探讨了不同影响因素下阿特拉津的降解动力学。结果表明:阿特拉津降解反应近似符合二级反应动力学,反应速率常数0.001 08~0.002 73 L·(mg·min)~(-1)。在纳米铁/活性炭复合材料去除阿特拉津过程中,纳米铁的还原和活性炭的吸附共同作用。     

Fenton试剂催化氧化嘧啶废水的特性

研究了Fenton催化氧化法对废水中嘧啶的去除效能,优化了处理体系中的反应条件,分析了各影响因子的作用机理;并用一元线性回归方程对不同温度下,嘧啶相对残余浓度对反应时间的相关性进行了定量分析。结果表明:温度为25℃,pH为3.5,Fe²⁺的投加量64 mmol/L,H₂O₂投加量为300 mmol/L时,反应2 h,Fenton试剂对嘧啶和COD的去除率分别达90%和50%以上;同时发现Fenton试剂对嘧啶的氧化降解具有相对优先性,且符合一级反应动力学模式,并计算表观反应速率常数和活化能。     

微气泡曝气 O3/ H2O2处理 RO 浓水的效能及影响因素简

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、H₂O₂/O₃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H₂O₂能提高臭氧氧化RO浓水的效果,H₂O₂/O₃初始摩尔比在0~0.8范围内,COD的去除率先增加后下降,H₂O₂/O₃初始摩尔比为0.5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H₂O₂/O₃初始摩尔比为0.5、溶液pH为8~9、臭氧浓度为80~100 mg/L、温度为10~28℃条件下,对COD为90~140 mg/L的RO浓水氧化处理4~10 h,出水COD维持在39.9~49.9 mg/L,达到《城镇污水处理厂污染物排放标准（GB 18918-2002）》中的一级A标准;去除1 g COD消耗O₃ 1.4~3.3 g,消耗O₃与H₂O₂的总氧量为2.2~4.4 g。     

活性炭纤维上4-氯酚及焦化废水尾水的O3催化氧化降解实验研究

选择YT-1000型活性炭纤维（ACF）作为催化剂,考察ACF与O₃协同作用催化降解水溶液中4-氯酚的最佳反应条件,并将该条件应用于焦化废水生物处理尾水中难降解有机污染物的催化氧化。ACF表面具有丰富的微孔结构,对4-氯酚有良好的吸附作用,在动力学上提高了其与O3反应的起始浓度,并且在ACF表面含氧、含氮等基团的催化作用下发生氧化反应,1 L浓度为100 mg/L的4-氯酚水样中投加2 g ACF反应6 min时,吸附作用对TOC的去除率为43.4%,而ACF协同O₃作用时的TOC去除率提高到72.5%,协同增效作用为67.1%;在选定的反应条件下,ACF协同O₃降解焦化废水生物处理尾水,60 min时的TOC与色度的去除率分别达到56.8%和96.3%。上述研究过程证明了吸附作用与催化作用的协同能有效降解生物过程不能降解的焦化废水中惰性有机污染物。     

UASB反应器对芳香族化合物反硝化降解特性研究

以苯、联苯和萘为模型化合物,研究了上流式厌氧污泥床反应器(UASB)在反硝化连续流运行条件下对含上述污染物废水的处理效果,并以葡萄糖为补充碳源,考察了COD/NO^-₃-N(简称C/N)比对有机物反硝化降解特性的影响。研究结果表明,当进水COD浓度约为900 mg/L,苯、联苯和萘总浓度约为60 mg/L,NO^-₃-N为20～60 mg/L时,UASB反应器能够在硝酸盐还原条件下稳定去除废水中有机污染物,其中COD平均去除率可达到85%,苯、萘和联苯平均去除率分别为90%、81%和71%。3种芳香烃反硝化降解速率顺序为苯>萘>联苯。 C/N比对苯的降解影响不十分显著,在C/N为5～30范围内,苯的去除率稳定在87%～92%;萘和联苯去除率受C/N影响较大,在C/N比为15时萘和联苯的去除率均达到最大,分别为82%和77%。     

Phytoremediation potential of the novel atrazine tolerant Lolium multiflorum and studies on the mechanisms involved

Atrazine impact on human health and the environment have been extensively studied. Phytoremediation emerged as a low cost, environmental friendly biotechnological solution for atrazine pollution in soil and water. In vitro atrazine tolerance assays were performed and Lolium multiflorum was found as a novel tolerant species, able to germinate and grow in the presence of 1 mg kg⁻¹ of the herbicide. L. multiflorum presented 20% higher atrazine removal capacity than the natural attenuation, with high initial degradation rate in microcosms. The mechanisms involved in atrazine tolerance such as mutation in psbA gene, enzymatic detoxification via P₄₅₀ or chemical hydrolysis through benzoxazinones were evaluated. It was demonstrated that atrazine tolerance is conferred by enhanced enzymatic detoxification via P₄₅₀. Due to its atrazine degradation capacity in soil and its agronomical properties, L. multiflorum is a candidate for designing phytoremediation strategies for atrazine contaminated agricultural soils, especially those involving run-off avoiding.     

Nitrogen limited biobarriers remove atrazine from contaminated water: laboratory studies

Atrazine is one of the most frequently used herbicides. This usage coupled with its mobility and recalcitrant nature in deeper soils and aquifers makes it a frequently encountered groundwater contaminant. We formed biobarriers in sand filled columns by coating the sand with soybean oil; after which, we inoculated the barriers with a consortium of atrazine-degrading microorganisms and evaluated the ability of the barriers to remove atrazine from a simulated groundwater containing 1 mg L(-1) atrazine. The soybean oil provided a carbon rich and nitrogen poor substrate to the microbial consortium. Under these nitrogen-limiting conditions it was hypothesized that bacteria capable of using atrazine as a source of nitrogen would remove atrazine from the flowing water. Our hypothesis proved correct and the biobarriers were effective at removing atrazine when the nitrogen content of the influent water was low. Levels of atrazine in the biobarrier effluents declined with time and by the 24th week of the study no detectable atrazine was present (limit of detection<0.005 mg L(-1)). Larger amounts of atrazine were also removed by the biobarriers; when biobarriers were fed 16.3 mg L(-1) atrazine 97% was degraded. When nitrate (5 mg L(-1) N), an alternate source of nitrogen, was added to the influent water the atrazine removal efficiency of the barriers was reduced by almost 60%. This result supports the hypothesis that atrazine was degraded as a source of nitrogen. Poisoning of the biobarriers with mercury chloride resulted in an immediate and large increase in the amount of atrazine in the barrier effluents confirming that biological activity and not abiotic factors were responsible for most of the atrazine degradation. The presence of hydroxyatrazine in the barrier effluents indicated that dehalogenation was one of the pathways of atrazine degradation. Permeable barriers might be formed in-situ by the injection of innocuous vegetable oil emulsions into an aquifer or sandy soil and used to remove atrazine from a contaminated groundwater or to protect groundwater from an atrazine spill.     

Degradation of atrazine in mineral salts medium and soil using enrichment culture

Atrazine degrading enrichment culture was prepared by its repeated addition to an alluvial soil and its ability to degrade atrazine in mineral salts medium and soil was studied. Enrichment culture utilized atrazine as a sole source of carbon and nitrogen in mineral salts medium and degradation slowed down when sucrose and/or ammonium hydrogen phosphate were supplemented as additional source of carbon and nitrogen, respectively. Biuret was detected as the only metabolite of atrazine while deethylatrazine, deisopropyatrazine, hydroxyatrazine and cyanuric acid were never detected at any stage of degradation. Enrichment culture degraded atrazine in an alkaline alluvial soil while no degradation was observed in the acidic laterite soil. Enrichment culture was able to withstand high concentrations of atrazine (110 μg/g) in the alluvial soil as atrazine was completely degraded. Developed mixed culture has the ability to degrade atrazine and has potential application in decontamination of contaminated water and soil.     

Atrazine removal in agricultural infiltrate by bioaugmented polyvinyl alcohol immobilized and free Agrobacterium radiobacter J14a: a sand column study

Bench-scale sand column breakthrough experiments were conducted to examine atrazine removal in agricultural infiltrate by Agrobacterium radiobacter J14a (J14a) immobilized in phosphorylated-polyvinyl alcohol compared to free J14a cells. The effects of cell loading and infiltration rate on atrazine degradation and the loss of J14a were investigated. Four sets of experiments, (i) tracers, (ii) immobilized dead cells, (iii) immobilized cells, and (iv) free cells, were performed. The atrazine biodegradation at the cell loadings of 300, 600, and 900 mg dry cells L(-1) and the infiltration rates of 1, 3, and 6 cm d(-1) were tested for 5 column pore volumes (PV). The atrazine breakthrough results indicated that the immobilized dead cells significantly retarded atrazine transport. The atrazine removal efficiencies at the infiltration rates of 1, 3, and 6 cm d(-1) were 100%, 80-97%, and 50-70%, respectively. Atrazine degradation capacity for the immobilized cells was not significantly different from the free cells. Both infiltration rate and cell loading significantly affected atrazine removal for both cell systems. The bacterial loss from the immobilized cell system was 10-100 times less than that from the free cell system. For long-term tests at 50 PV, the immobilized cell system provided consistent atrazine removal efficiency while the atrazine removal by the free cells declined gradually because of the cell loss.     

Riboflavin-photosensitized degradation of atrazine in a freshwater environment

The effect of the photosensitizer riboflavin (0, 10, 50, 100 microM) on the fate of atrazine (10 mg/l) in a freshwater environment was studied. It was found that at 100 microM riboflavin significantly enhanced the degradation of atrazine and more than 80% of atrazine in a natural water environment was depleted in 72 h. The relative contribution of microbial assemblages and the freshwater matrix to the degradation of atrazine and the degradation kinetics of atrazine were compared under different experimental conditions. The products and pathways of atrazine transformation were studied with GC-MS and HPLC with a photodiode array detector. The results show that dealkylation and alkyl chain oxidation are involved in the degradation of atrazine.     

Biodegradation of atrazine by Rhodococcus sp. BCH2 to N-isopropylammelide with subsequent assessment of toxicity of biodegraded metabolites

Atrazine is a persistent organic pollutant in the environment which affects not only terrestrial and aquatic biota but also human health. Since its removal from the environment is needed, atrazine biodegradation is achieved in the present study using the bacterium Rhodococcus sp. BCH2 isolated from soil, long-term treated with atrazine. The bacterium was capable of degrading about 75 % atrazine in liquid medium having pH 7 under aerobic and dark condition within 7 days. The degradation ability of the bacterium at various temperatures (20–60 °C), pH (range 3–11), carbon (glucose, fructose, sucrose, starch, lactose, and maltose), and nitrogen (ammonium molybdate, sodium nitrate, potassium nitrate, and urea) sources were studied for triumph optimum atrazine degradation. The results indicate that atrazine degradation at higher concentrations (100 ppm) was pH and temperature dependent. However, glucose and potassium nitrate were optimum carbon and nitrogen source, respectively. Atrazine biodegradation analysis was carried out by using high-performance thin-layer chromatography (HPTLC), Fourier transform infrared spectroscopy (FTIR), and liquid chromatography quadrupole time-of-flight (LC/Q-TOF-MS) techniques. LC/Q-TOF-MS analysis revealed formation of various intermediate metabolites including hydroxyatrazine, N-isopropylammelide, deisopropylhydroxyatrazine, deethylatrazine, deisopropylatrazine, and deisopropyldeethylatrazine which was helpful to propose biochemical degradation pathway of atrazine. Furthermore, the toxicological studies of atrazine and its biodegraded metabolites were executed on earthworm Eisenia foetida as a model organism with respect to enzymatic (SOD and Catalase) antioxidant defense mechanism and lipid peroxidation studies. These results suggest innocuous degradation of atrazine by Rhodococcus sp. BCH2 in nontoxic form. Therefore the Rhodococcus sp.BCH2 could prove a valuable source for the eco-friendly biodegradation of atrazine pesticide.     

Alginate immobilized enrichment culture for atrazine degradation in soil and water system

An atrazine degrading enrichment culture, a consortium of bacteria of genus Bacillus along with Pseudomonas and Burkholderia, was immobilized in sodium alginate and was used to study atrazine degradation in mineral salts medium (MSM), soil and wastewater effluent. Sodium alginate immobilized consortium, when stored at room temperature (24 ± 5°C), was effective in degrading atrazine in MSM up to 90 days of storage. The survival of bacteria in alginate beads, based on colony formation unit (CFU) counts, suggested survival up to 90 days and population counts decreased to 1/5^th on 120 days. Comparison of atrazine degrading ability of the freely suspended enrichment culture and immobilized culture suggested that the immobilized culture took longer time for complete degradation of atrazine as a lag phase of 2 days was observed in the MSM inoculated with alginate immobilized culture. The free cells resulted in complete degradation of atrazine within 6 days, while immobilized cells took 10 days for 100% atrazine degradation. Further, immobilized cultures were able to degrade atrazine in soil and wastewater effluent. Alginate beads were stable and effective in degrading atrazine till 3rd transfer and disintegrated thereafter. The study suggested that immobilized enrichment culture, due to its better storage and application, can be used to degrade atrazine in soil water system.     

Performance Evaluation of Waste Activated Carbon on Atrazine Removal from Contaminated Water

Abstract

In this study, the potential of spent activated carbon from water purifier (Aqua Guard, India) for the removal of atrazine (2 chloro-4 ethylamino-6-isopropylamino-1, 3, 5 triazine) from wastewaters was evaluated. Different grades of spent activated carbon were prepared by various pretreatments. Based on kinetic and equilibrium study results, spent activated carbon with a grain size of 0.3–0.5 mm and washed with distilled water (designated as WAC) was selected for fixed column studies. Batch adsorption equilibrium data followed both Freundlich and Langmuir isotherm. Fixed bed adsorption column with spent activated carbon as adsorbent was used as a polishing unit for the removal of atrazine from the effluent of an upflow anaerobic sludge blanket (UASB) reactor treating atrazine bearing domestic wastewater. Growth of bacteria on the surface of WAC was observed during column study and bacterial activity enhanced the effectiveness of adsorbent on atrazine removal from wastewater.     

Performance evaluation of waste activated carbon on atrazine removal from contaminated water

In this study, the potential of spent activated carbon from water purifier (Aqua Guard, India) for the removal of atrazine (2 chloro-4 ethylamino-6-isopropylamino-1, 3, 5 triazine) from wastewaters was evaluated. Different grades of spent activated carbon were prepared by various pretreatments. Based on kinetic and equilibrium study results, spent activated carbon with a grain size of 0.3-0.5 mm and washed with distilled water (designated as WAC) was selected for fixed column studies. Batch adsorption equilibrium data followed both Freundlich and Langmuir isotherm. Fixed bed adsorption column with spent activated carbon as adsorbent was used as a polishing unit for the removal of atrazine from the effluent of an upflow anaerobic sludge blanket (UASB) reactor treating atrazine bearing domestic wastewater. Growth of bacteria on the surface of WAC was observed during column study and bacterial activity enhanced the effectiveness of adsorbent on atrazine removal from wastewater.