热活化过硫酸盐降解氧氟沙星特性及响应面优化

为了探究热活化过硫酸盐（PS）技术对水中氧氟沙星（OFX）的氧化降解作用,考察了反应温度、体系的初始pH、PS的初始浓度、OFX的初始浓度对OFX降解效果的影响;并在单因素实验的基础上,选取反应时间、体系的初始pH、PS的初始浓度和OFX的初始浓度4个因素进行了响应面优化实验。结果表明：最佳降解条件为,反应温度60℃、PS初始浓度4.0 mmol/L、pH=4.7、OFX初始浓度0.03 mmol/L、反应时间60 min,此时OFX的降解率为81.29%;4个因素对热活化PS降解OFX均有影响,其影响显著性从大到小为反应时间、OFX的初始浓度、PS的初始浓度、初始pH。利用响应曲面法模拟出反应体系的最佳条件,经实验验证,OFX降解率为93.78%,与预测最佳结果95.00%基本相符,表明模型可靠有效。     

二价铁活化过硫酸盐去除水中苯胺

零价铁和硝基苯反应后生成二价铁和苯胺,而苯胺也是地下水污染物。硫酸根自由基具有强氧化性,可以降解苯胺。而二价铁可以活化过硫酸盐产生硫酸根自由基,进而去除苯胺。本文研究了二价铁浓度、过硫酸盐浓度、苯胺初始浓度、体系初始pH、反应温度等因素对二价铁活化过硫酸盐去除水中苯胺处理效率的影响。结果表明:1)Fe2+活化过硫酸盐生成SO-4·能快速并有效氧化降解苯胺,对于目标浓度为1 000 mg/L的苯胺而言,Fe2+浓度为3.3 mmol/L,Na2S2O8浓度为4.4 mmol/L时,对苯胺有较佳降解效果,苯胺的降解率为86.33%。2体系对较低浓度的苯胺降解效果较好,当污染物初始浓度由1 000 mg/L降低到500 mg/L和100 mg/L时,苯胺降解率由86.33%升高为90.27%和97.16%。3初始pH对苯胺的降解率影响较大,中性条件下(pH=7左右)降解率较好,高初始pH(pH=9,11)和低初始pH条件(pH=3,5)下均低于中性条件下苯胺的降解效率。4体系的温度变化对降解率影响不明显。     

以改性蛭石为填料的生物流化床法处理低C /N污水的应用

以热改性蛭石为填料,提高生物流化床系统处理低C/N污水的能力。实验结果表明,经过改性的蛭石对氨氮和COD的去除效率有明显的提高,分别是天然蛭石的2.1倍和2.7倍。在热改性蛭石为填料的生物流化床系统处理低C/N污水的实验过程中,主要分析了温度、pH和DO对反应系统处理效果的影响,确定了反应器的最佳处理条件。对于氨氮质量浓度为50 mg/L、ρ(COD)为200 mg/L的原水,在温度为30℃、pH=8.0、ρ(DO)=2.0 mg/L的处理条件下,反应系统对氨氮和COD的处理效果最佳,去除率分别可达94.9%和85.7%。     

花岗岩母质红壤吸附水中砷(Ⅴ)的影响因素试验

为探讨花岗岩母质红壤吸附水中砷(Ⅴ)的效果和机理, 采用静态吸附实验, 研究溶液砷初始浓度、反应时间、温度、pH值等因素对红壤吸附水中砷的影响.当溶液砷初始浓度小于5.0 mg/L时, 红壤对砷的去除率均大于97%;随着砷初始浓度增大, 去除率逐渐降低; 反应初期(0~120 min), 红壤对砷的去除率迅速增大至95.0%左右.此后, 去除率缓慢增大, 直到720 min后, 去除率达到97.0%左右, 并趋于稳定; 在砷初始浓度一定时, 红壤对砷的吸附量随着温度的升高逐渐增加, 但增加幅度较小; 红壤对砷的去除率随着体系pH值的增大呈减小趋势; 正交试验表明, 在砷初始浓度为5.0 mg·L-1、反应时间为120 min、pH为5.0及反应温度为40℃的组合下, 红壤对砷的去除率最大.      

臭氧化含苯酚污水投加水镁石沉淀出草酸镁的实验研究

本文通过两组不同水镁石-苯酚投料比的实验,研究固体沉淀物与水质变化的关系。实验显示,水镁石解离出的Mg²⁺与苯酚降解的中间产物能形成难溶盐,并发生沉淀分离,促进含苯酚废水臭氧化降解的效率。当苯酚的初始浓度为47 g/L,初始碳镁原子比(C/Mg)为30时,经3小时充分臭氧化曝气后,投加的水镁石全部耗尽。XRD、TG/DSC结果显示新形成的沉淀物为草酸镁。反应终点的pH值在4以下,TOC去除率为40%。当体系的初始C/Mg(原子比)为1,苯酚的初始浓度为1.5 g/L时,同样的臭氧化曝气过程体系残留的沉淀物仍是水镁石。反应终点的pH值在10左右,TOC去除率为92.8%。研究证明,苯酚臭氧化过程也是体系酸化的过程,至少在高C/Mg比条件下新生的质子能与水镁石解离出的羟基中和,水镁石解离出的Mg²⁺可与草酸根结合沉淀出草酸镁。     

Degradation of phenol of high concentration by FeAIOx/MMT catalyzed Fenton reaction

以蒙脱土为载体制备负载型Fe/Al复合氧化物（FeAlOx/MMT）用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

紫外/氯工艺对水中微囊藻毒素的去除

水体富营养化导致藻类的爆发进而引起藻毒素的释放。微囊藻毒素(MCLR)是最为常见的藻毒素,具有很强的毒性,对人类健康具有潜在危害。本文采用紫外/氯组合工艺,研究其对水中微囊藻毒素的控制效果。结果表明：紫外/氯共同作用下能够产生·Cl、·OH等活性自由基,具有协同降解MCLR的作用,30 min即可实现MCLR的完全去除,其降解效率随着氯投加质量浓度的增加而升高。在酸性及中性条件下,pH的变化对紫外/氯降解MCLR没有影响;在碱性条件下,MCLR的降解效率随pH的升高显著降低,pH升高至9时,30 min MCLR的降解效率仅为41.3%。此外,不同的水样来源和水质特点对紫外/氯联合降解MCLR的效率具有显著影响,纯水、西湖水及水厂滤后水的30 min去除率分别为99.5%,40.2%及63.3%。MCLR 的降解效率随腐殖酸质量浓度增大而降低,在60 min作用时间内,不含腐殖酸水样的MCLR去除率高达99.5%,当腐殖酸质量浓度增加到10 mg/L时,MCLR去除率仅为45.3%。     

硅藻土-无定形碳-氧化铁三元复合体系降解三硝基甲苯的研究

煤系共伴生非金属矿产开发及综合利用难度大。本文针对先锋褐煤共伴生硅藻土高有机质、高铁的特点,提出硅藻土原矿经提纯处理后,在N2作为保护气氛下,高温煅烧形成硅藻土-无定形碳-氧化铁三元复合材料,在类Fenton体系下,去除TNT污染物的开发利用技术路线。本文考察了硅藻土处理条件、反应时间、H2O2浓度、三元复合硅藻土投加量、pH值等因素对TNT降解效能的影响。研究表明三元复合硅藻土对TNT吸附降解的最佳工艺条件为:硅藻土用量为2 g/L,H2O2(30%)4 m L/L,pH值1,反应时间2.5 h。该工艺条件下,50 mg/L TNT去除率为98%。     

坡缕石粘土固定辣根过氧化酶处理硝基酚废水

以坡缕石粘土、淀粉、水玻璃为原料,研究了固定化酶载体的制备工艺,探究了固定化酶载体在辣根过氧化酶(HRP)降解硝基酚废水中的作用,并探讨了反应时间、酶浓度、H2O2及硝基酚浓度对降解效果的影响。结果表明,固定化酶载体的最佳制备工艺为:水玻璃12%,淀粉20%,煅烧温度550℃,煅烧时间2 h;固定化酶对硝基酚的去除效果明显高于原酶;固定化酶去除水中硝基酚的最佳反应条件为:反应时间1.5 h,加酶量150 U,H2O2浓度0.12%,硝基酚浓度100 mg/L;固定化酶重复使用7次后对硝基酚的去除率仍高于60%。     

羟基磷灰石吸附水溶液中Cd~(2 )的影响因素的研究

对羟基磷灰石 (Hap)固定水溶性Cd2 的影响因素进行了较为系统的实验研究。实验表明 :去除率与Cd2 初始浓度呈负相关 ,在Cd2 初始浓度 <10mg/L时 ,与作用时间、pH值、Hap用量呈正相关 ,温度对去除率的影响较小。通过正交实验确定了最佳吸附条件 :Hap用量为 5g/L ,pH值为 6 ,作用时间 5min。     

Fe/Ag催化臭氧氧化降解苯酚的研究

为研究双金属催化剂去除有机污染物的效果,采用自制Fe/Ag催化剂对模拟苯酚废水进行了臭氧催化氧化处理。通过扫描电子显微镜(SEM)、比表面积分析仪(BET)和X射线衍射(XRD)对催化剂进行表征,并考察了催化剂类型、催化剂投加量和溶液初始pH值对降解效果的影响规律。结果表明:与Fe相比,Fe/Ag比表面积减少了22.8%,在Fe/Ag/O₃与含苯酚废水的反应体系中,反应遵循臭氧直接作用和活性自由基(·OH、·O₂、H₂O₂)共同作用的机理;Fe/Ag在反应过程中体现出良好的协同作用;300 mg/L的苯酚模拟废水在pH=6.3、Fe/Ag投加量为1.00 g的最优反应条件下经60 min反应,苯酚与化学需氧量(COD)去除率比单独臭氧氧化分别提高了18.4%和29.4%。     

氧协同菱铁矿降解微囊藻毒素机理研究

已知在无氧条件下天然矿物菱铁矿能成功水解微囊藻毒素-LR(MC-LR),然而实际应用过程中难以避免水中溶解氧(O₂)的存在,因此有必要深入研究不同溶氧量(DOC)条件下菱铁矿对MC-LR降解的影响。本文通过在无氧和有氧条件下菱铁矿对MC-LR的降解实验,发现在有氧条件下(溶氧量1.62～21.87 mg/L), MC-LR的降解速率均比无氧条件(k₀=0.030 16 mg·L^-1·h^-1)高且其降解速率随O₂含量增加而依次增加,当O₂加入量为1.0 mL(溶氧量21.87 mg/L)时,菱铁矿对MC-LR降解速率最大(0.083 34 mg·L^-1·h^-1),为无氧条件下的2.76倍。通过外加腐殖酸(humic acid, HA)和自由基进行捕获实验,发现FeCO₃能直接活化O₂产生超氧自由基(·O~-₂),以实现对MC-LR的氧化,但外加HA抑...     

冻融作用对垃圾填埋场防渗层性能的影响

建立系列模拟实验研究了冻融作用对垃圾填埋场防渗层防渗和去污性能的影响。实验结果表明：冻融作用对垃圾填埋场防渗层有一定的破坏作用,对渗透系数和污染物的去除能力均有重要影响;冻融前的渗透系数均低于国家标准（1.0×10^-7 cm/s）,冻融后防渗层的渗透系数增加2～6倍;防渗层对COD、Cl^-和NH⁺₄的去除率分别从冻融前的68.6%、31.6％和70.5％变为86.2%、18.2％和23.0％。     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

南堡凹陷原油高分辨质谱特征及其地球化学意义

南堡凹陷深部油气资源丰富, 油气成因研究薄弱.首次采用高分辨质谱(负离子电喷雾离子源(electrospray ionization, 简称ESI)傅里叶变换离子回旋共振质谱(Fourier transform ion cyclotron resonance mass spectrometry, 简称FT-ICR MS)技术对南堡凹陷原油中杂原子化合物的组成与分布特征及其地球化学意义进行了研究.应用负离子ESI FT-ICR MS检测出9种主要杂原子组合类型, 分别为N₁、N₁O₁、N₁O₂、N₁O₃、N₂、O₁、O₂、O₃和O₄类, 其中N₁、O₁和O₂类在所有样品中普遍存在且相对丰度较高.经研究发现成熟度对原油中N₁、O₁类化合物碳数分布、缩合度有明显的控制作用.实验观察到N₁类DBE(等效双键数)=12, 15的高低分子量同系物相对丰度参数C_16-20/C_21-50-DBE₁₂-N₁和C_20-24/C_25-50-DBE₁₅-N₁、N₁类缩合度参数DBE₁₂/DBE₉-N₁及O₁类缩合度参数DBE_8-9/DBE₄-O₁与成熟度指标Ts/Tm、TMNr具有良好的相关性, 认为它们可作为该区原油成熟度评价指标, 反映烃类演化的热动力学原理.南堡凹陷不同层系原油高分辨质谱特征有明显差异, 指示其可应用于母源岩性质识别.综合研究认为, FT-ICR MS在成熟度评价、油气成因与油源识别等方面地球化学意义显著, 其在油气地球化学理论研究和油气勘探中具有潜在的应用价值.      

电化学循环井驱动模拟含水层化学氧化降解三氯乙烯

传统原位化学氧化地下水修复技术存在氧化剂迁移距离短和利用率低等问题。本研究在双井循环模式促进传质的基础上,通过注水井中的地下水电解原位提供O₂和H₂,配合乙二胺四乙酸(ethylenediamine tetraacetic acid,EDTA)络合溶解出含水层Fe(Ⅱ),活化O₂产生羟基自由基(•OH),实现地下水三氯乙烯(TCE)的氧化降解。在填充了砂土和黏土互层的二维砂槽中,设置电流为0.2 A、流速为72 cm/d、初始TCE浓度为3 mg/L,经过9 d的连续通电处理后,TCE浓度降低到1 mg/L,降解率达到67%。通电前投加0.5 mmol/L EDTA,经过1 d水流循环后含水层中溶解态Fe(Ⅱ)浓度从02 mg/L增加到414 mg/L,黏土区域较高。通电过程中,循环井促进O₂、Fe(Ⅱ)-EDTA和TCE的有效接触与反应,使TCE氧化降解。通电初期,黏土区域Fe(Ⅱ)氧化速率、TCE降解速率较周围慢,后期差异逐渐减小。未通电时加入醋酸钠可促进Fe(Ⅲ)还原,使含水层中铁循环利用。该修复过程通过循环井提升了氧化剂迁移距离,使用源于含水层的Fe(Ⅱ)-EDTA和稳定性较好的O₂提高了氧化剂利用率,有望应用于有机污染地下水修复。     

Comparison of Fenton,ultraviolet–Fenton and ultrasonic–Fenton processes on organics and colour removal from pre-treated natural gas produced water

Produced water (PW) from natural gas field, characterized with high organic contents, has brought high environmental concerns world widely. Fenton and enhanced Fenton technologies were considered as the potential methods to degrade the organic contaminates in the PW, but with very limited data or reference. Here, we examined the optimum conditions of Fenton on organics and colour removal from natural gas PW after coagulation pre-treatment. Simultaneously, the optimal Fenton process integrated with ultraviolet (UV) and ultrasonic (US) irradiation were applied to enhance pollutants removal efficiencies. The optimal Fenton conditions were found at 60 min with molar ratios of 6:1 and 25:1 for H₂O₂/COD and H₂O₂/Fe²⁺, respectively and the initial pH of 3. Among these the three treatment processes, chemical oxygen demand (COD), total organic carbon, 5-day biological oxygen demand (BOD₅), and colour removal efficiencies were highest during UV–Fenton (82, 73, 68, and 95%,) followed by US–Fenton (79, 70, 66, and 95%) and Fenton treatment (70, 58, 51, and 92%), respectively. High biodegradability (BOD₅/COD) was also observed after UV–Fenton process (0.76) than the others (both 0.73). The current study showed a satisfactory carbon and colour removal efficiencies from PW using different Fenton processes; however, there still is a need for final polishing such as biological treatment or low cost constructed wetland before discharge. This study can be a good reference for engineering application PW treatment.     

UV/H2O2法降解乙酸影响因素的研究

通过采用UV/H₂O₂法,以乙酸为研究对象,高压汞灯为光源,在温度为（35±2）℃、曝空气量为0.8 L/min的条件下,研究了UV/H₂O₂技术对500 mL浓度为8 mmol/L的乙酸溶液进行的光降解反应。考察了各种因素对UV/H₂O₂降解乙酸的影响。实验表明,H₂O₂浓度为15 mmol/L、pH值为3.4时,乙酸降解效果最佳,此时,在240 min内,乙酸、TOC和COD的去除率可分别达到98%、98%和97%,体系中乙酸完全矿化。利用UV/H₂O₂法对实际糠醛废水进行了降解,效果良好。     

固体停留时间对HLB-MR反应器直接回收城市污水中有机物的影响

为优化高负荷生物絮凝-膜反应器（HLB-MR）的工艺参数,提高其资源化城市污水的效能,采用平行对比实验,考察了不同固体停留时间（t_SR）条件下反应器的有机物去除效率、生物絮凝效果、有机物回收效果和膜污染情况。结果表明：在t_SR分别为0.2、0.6、1.0 d时,HLB-MR反应器有机物去除效率均在85%以上,其出水化学需氧量（COD）质量浓度均保持在30 mg/L左右;反应器内的生物絮凝效果随着t_SR的延长而增强,其胶体COD絮凝效率从t_SR为0.2 d时的66%增加到t_SR为1.0 d时的95%,与此同时,有机物的矿化损失率也逐渐增加,从t_SR为0.2 d时的6.9%增加到t_SR为1.0 d时的10.5%,总COD的回收率逐渐降低;反应器内浓缩液的膜污染潜势随着t_SR的延长逐渐缓解,这与较长t_SR条件下反应器内胞外聚合物（EPS）产量较高、生物絮凝效果较好、微细颗粒（0~1 μm）的颗粒浓度较低有关。经过综合对比分析,0.6 d为反应器较优的t_SR参数,在该条件下,胶体COD的絮凝效率高达90%,膜污染程度较轻;总COD的矿化损失率低至7.4%,总COD的回收率（忽略膜清洗时有机物损失）可高达80%以上。     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.