Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

Enhanced reductive degradation of carbon tetrachloride by carbon dioxide radical anion-based sodium percarbonate/Fe(II)/formic acid system in aqueous solution

Complete CT degradation was achieved by SPC/Fe(II)/FA system.Formic acid established the reductive circumstance by producing CO₂·^–.CO₂·^– was the dominant active species responsible for CT degradation.CT degradation was favorable in the pH range from 3.0 to 9.0.SPC/Fe(II)/FA system may be suitable for CT remediation in contaminated groundwater.The performance of sodium percarbonate (SPC) activated with ferrous ion (Fe(II)) with the addition of formic acid (FA) to stimulate the degradation of carbon tetrachloride (CT) was investigated. Results showed that CT could be entirely reduced within 15 min in the system at a variety of SPC/Fe(II)/FA/CT molar ratios in experimental level. Scavenging tests indicated that carbon dioxide radical anion (CO2·^–) was the dominant reactive oxygen species responsible for CT degradation. CT degradation rate, to a large extent, increased with increasing dosages of chemical agents and the optimal molar ratio of SPC/Fe(II)/FA/CT was set as 60/60/60/1. The initial concentration of CT can hardly affect the CT removal, while CT degradation was favorable in the pH range of 3.0–9.0, but apparently inhibited at pH 12. Cl^– and HCO₃^– of high concentration showed negative impact on CT removal. Cl^– released from CT was detected and the results confirmed nearly complete mineralization of CT. CT degradation was proposed by reductive C-Cl bond splitting. This study demonstrated that SPC activated with Fe(II) with the addition of FA may be promising technique for CT remediation in contaminated groundwater.     

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe(III) in the presence of citric acid

Trichloroethene (TCE) degradation by Fe(III)-activated calcium peroxide (CP) in the presence of citric acid (CA) in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concentration of soluble Fe(III) and promoting H₂O₂ generation. The generation of HO? and O₂^-? in both the CP/Fe(III) and CP/Fe(III)/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly to direct oxidation by HO?, while O₂^-? strengthened the generation of HO? by promoting Fe(III) transformation in the CP/Fe(III)/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl^-, HCO₃^-, and humic acid (HA) inhibited TCE degradation to different extents for the CP/Fe(III)/CA system. Analysis of Cl^- production suggested that TCE degradation in the CP/Fe(III)/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe(III)-activated calcium peroxide for treating TCE contaminated groundwater.     

Degradation of carbon tetrachloride in thermally activated persulfate system in the presence of formic acid

The thermally activated persulfate (PS) degradation of carbon tetrachloride (CT) in the presence of formic acid (FA) was investigated. The results indicated that CT degradation followed a zero order kinetic model, and CO ₂ ^– · was responsible for the degradation of CT confirmed by radical scavenger tests. CT degradation rate increased with increasing PS or FA dosage, and the initial CT had no effect on CT degradation rate. However, the initial solution pH had effect on the degradation of CT, and the best CT degradation occurred at initial pH 6. Cl^– had a negative effect on CT degradation, and high concentration of Cl^– displayed much strong inhibition. Ten mmol·L^–1HCO ₃ ^– promoted CT degradation, while 100 mmol·L^–1NO ₃ ^– inhibited the degradation of CT, but SO ₄ ^2– promoted CT degradation in the presence of FA. The measured Cl–concentration released into solution along with CT degradation was 75.8% of the total theoretical dechlorination yield, but no chlorinated intermediates were detected. The split of C-Cl was proposed as the possible reaction pathways in CT degradation. In conclusion, this study strongly demonstrated that the thermally activated PS system in the presence of FA is a promising technique in in situ chemical oxidation (ISCO) remediation for CT contaminated site.     

Investigation of the effects of humic acid and H 2 O 2 on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s⁻¹, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

柠檬酸对生物炭钝化污染土壤中重金属稳定性的影响

为了研究生物炭(BC)对重金属复合污染土壤的钝化效果以及环境条件变化后钝化产物的稳定性.在受Cd、Pb和Zn污染的土壤中添加不同比例的生物炭进行土培实验,两个月后,添加不同浓度的柠檬酸模拟植物根际环境条件,分析土壤环境条件变化后重金属钝化产物的稳定性.结果表明,与对照组相比,添加生物炭(5%和8%)显著提高了土壤的pH值、阳离子交换容量(CEC)、土壤有机质(SOM),而有效态重金属和重金属毒性浸出浓度均显著降低,且后者低于其国际标准.添加柠檬酸后,土壤pH值随柠檬酸浓度的增加呈现下降趋势;生物炭的添加比例一定时,有效态Cd(DTPA-Cd)和Cd的毒性浸出浓度(TCLP-Cd)随柠檬酸浓度的增加呈现先降低(2 mmol·kg~(-1))后升高(10、20 mmol·kg~(-1))的趋势,而有效铅(DTPA-Pb)和有效态锌(DTPA-Zn)随柠檬酸浓度的增加而上升.柠檬酸浓度一定时,有效态重金属和重金属毒性浸出浓度随生物炭的添加比例的增加而降低,当生物炭的添加比例大于5%时,TCLP-Cd和TCLP-Zn虽有所上升(与无柠檬酸相比),但均低于其国际标准.可见,生物炭可对重金属污染土壤进行有效修复,但随着环境条件的变化,被钝化的重金属会发生解吸和溶解释放,从而增强其生物有效性和环境风险,但当生物炭的添加比例较高时,会一定程度抑制重金属的解吸和溶解释放,Cd和Zn的环境风险仍处于可接受的安全水平.     

柠檬酸促进土壤镉解吸的机理研究

以人工致污的广东红壤为材料,采用平衡批处理法研究了不同浓度及不同pH值的柠檬酸溶液对土壤中重金属镉解吸产生的影响,并对处理前后的土样进行了镉的形态分析。研究结果表明:柠檬酸可以促进土壤镉的解吸且促进作用随着柠檬酸浓度的增加而增加;随着溶液pH的变化,溶液中柠檬酸的形态发生变化,导致其络合土壤镉的能力发生变化;与原土相比,经过柠檬酸处理后土样中的酸可提取态镉所占比例下降,说明柠檬酸对土壤镉解吸的部分主要来自酸可提取态。     

柠檬酸促进土壤镉解吸的机理研究

以人工致污的广东红壤为材料,采用平衡批处理法研究了不同浓度及不同pH值的柠檬酸溶液对土壤中重金属镉解吸产生的影响,并对处理前后的土样进行了镉的形态分析。研究结果表明：柠檬酸可以促进土壤镉的解吸且促进作用随着柠檬酸浓度的增加而增加;随着溶液pH的变化,溶液中柠檬酸的形态发生变化,导致其络合土壤镉的能力发生变化;与原土相比,经过柠檬酸处理后土样中的酸可提取态镉所占比例下降,说明柠檬酸对土壤镉解吸的部分主要来自酸可提取态。     

柠檬酸存在下酸性土壤中铝溶解动力学的初步研究

用一次平衡法研究了柠檬酸存在下砖红壤和红壤中铝的溶解动力学并与高岭石的结果进行比较，结果表明土壤铝的溶解速率比高岭石中的大得多，这主要因为土壤中交换态铝和无定形氧化铝的溶解速率较快，而粘土矿物中铝的溶解速率比较缓慢。红壤中硅、铝释放量的比较证明了这一假设，反应41．5h，硅的释放量仅为铝的8％。48h内铝的溶解动力学曲线可分为3个阶段：0-30min的快反应阶段，主要是土壤交换态铝和结晶不良的氧化铝的溶解；30-120min的较快反应阶段，主要是铝氧化物的溶解；120min后的慢反应阶段，主要是氧化铝和粘土矿物中铝的溶解。     

Visible light photocatalytic degradation of microplastic residues with zinc oxide nanorods

Microplastics have recently become a major environmental issue due to their ubiquitous distribution, uncontrolled environmental occurrences, small sizes and long lifetimes. Actual remediation methods include filtration, incineration and advanced oxidation processes such as ozonation, but those methods require high energy or generate unwanted by-products. Here we tested the degradation of fragmented, low-density polyethylene (LDPE) microplastic residues, by visible light-induced heterogeneous photocatalysis activated by zinc oxide nanorods. The reaction was monitored using Fourier-transform infrared spectroscopy, dynamic mechanical analyser and optical imaging. Results show a 30% increase of the carbonyl index of residues, and an increase of brittleness accompanied by a large number of wrinkles, cracks and cavities on the surface. The degree of oxidation was directly proportional to the catalyst surface area. A mechanism for polyethylene degradation is proposed.

     

Feasibility of metabolic parameter estimation in pharmacokinetic models of carbon tetrachloride exposure in rats1

Carbon tetrachloride (CCl₄) is a toxic chemical that was once used in degreasers and detergents, and some remnants of the chemical may be present in the water supply. Physiologically-based pharmacokinetic (PBPK) modeling can assist in understanding resulting internal doses of CCl₄ after exposure, but the pharmacokinetic parameters describing the metabolism of CCl₄ are not well characterized. The goal of this study was to provide insights into how to more accurately estimate these values in rats using PBPK modeling and data from previous studies. Three different PBPK models were constructed to describe CCl₄ exposure in rats via inhalation, oral ingestion, and venous injection. Each of these models was compared to data, and sensitivity analysis was performed for each model to determine whether the available data could be used to accurately determine the metabolic parameters of interest. These parameter sensitivities were so low that optimization to the available data yielded physiologically unrealistic results. Model sensitivities were analyzed for different doses and routes of exposure in order to find experimental conditions that would allow for greater identifiability of the metabolic parameters. Data were simulated from these models at optimal conditions with varying levels of noise from a normal distribution. Optimizations were then performed to confirm that the original values could be obtained. The experiments developed are left as suggestions for investigators who wish to further pursue estimating these metabolic parameters.     

纳米TiO2光催化降解有机磷农药的研究

通过实验,探讨了用纳米TiO2光催化处理有机磷农药模拟废水和实际应用的有机磷农药的可行性.实验表明,以测定不同时间PO43-的浓度来衡量有机磷的降解率,并以此来衡量有机磷农药及其中间产物降解的程度是合理的.光催化降解甲胺磷和水胺硫磷的结果,显示了有机磷农药的降解率与其结构有关.实际应用的有机磷农药也可用光催化降解.     

零价铝/酸体系对活性黑染料脱色降解的强化

采用零价铝/酸体系(Zero valent-aluminum acid system)处理活性黑5染料溶液.以活性黑5在特征吸收波长595 nm的吸光度变化为分析指标,考察了Fe0、Fe2+、Fe3+、多金属氧酸盐(POM)对染料溶液脱色的强化过程.结果表明,在摇床转速175 r·min-1、p H 2.5、25℃和铝粉投加量为2 g·L-1条件下,低剂量的铁源对零价铝/酸体系具有促进的作用,提高了零价铝/酸体系对活性黑5的降解脱色效率,当外加铁源达到一定的量时,这种加强作用会减弱.在0—0.50 mmol·L-1范围内,POM加入后的拟一级反应速率常数是POM加入前的1.46倍,去除率从75%提高到95%.活性黑5的降解符合拟一级反应动力学模型.     

生物炭载硫化铁对2,4-二氯苯氧乙酸的催化氧化降解

以木质生物炭为载体制备了负载型硫化铁(FeS_x/BC),采用扫描电镜/能量色散X射线光谱(SEM/EDX)、X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对其结构进行了表征分析.然后将其用于催化除草剂2,4-二氯苯氧乙酸(2,4-D)的类Fenton氧化降解,并与市售硫化亚铁(c-FeS)进行对比.结果表明,生物炭可以提高硫化铁分散性,炭载催化剂中的Fe主要以Fe_3S_4形式存在.与c-FeS相比,采用FeS_x/BC催化降解2,4-D的反应速率常数(k_(obs))提高了约20倍.降解反应速率随催化剂、H_2O_2用量增加而提高,但是随初始pH(2.0—9.0)上升而下降.机理研究表明,生物炭作为电子穿梭体有助于提高·OH的生成量,促进2,4-D降解中间产物转化、并使脱氯反应更完全.     

Anaerobic degradation kinetics of reactive dye with different carbon sources

This study aims to investigate the anaerobic degradation kinetics of reactive dye, C.I. Reactive Red 141 (Evercion Red H-E7B) by partially granulated anaerobic mixed culture using three carbon sources, namely modified starch (MS), polyvinyl alcohol (PVA) and acrylic size (AS) during batch incubation. There is a first-order kinetics reaction in the decolorization processes using MS and PVA as carbon sources, while a zero-order kinetics relationship describes the decolorization process for the AS carbon source. The k values and color removal rate of decolorization with MS carbon source was higher than those of PVA and AS carbon sources. This is because the MS carbon source was well degraded in comparison to AS and PVA, respectively This study also found dye reduction could be enhanced through the addition of MS as a carbon source. The decolorization rates increased with decrease in dye concentrations of RR 141. In contrast, the decolorization rates increased with increase in COD concentration.     

不同pH的柠檬酸对茶园土壤溶出液中氟组分变化的影响

通过连续流动搅拌法,研究了不同pH的柠檬酸对茶园土壤溶出液中氟组分变化的影响.结果表明,土壤溶出液的pH随溶出时间的延长而逐渐减小.土壤溶出液中的游离态氟和总氟的浓度随时间的延长和柠檬酸pH的升高而逐渐减小,且呈现初始(0—6h)溶出浓度较高,而后(6—10h)逐渐减缓的趋势.土壤氟的溶出过程用一级动力学方程、Elovich方程、扩散方程和双常数方程均有较好的拟合,决定系数(R2)均大于0.90.低pH(pH3.5)条件下,F主要以H-F形态存在,随着pH的升高(pH4.0—5.0),H-F形态的氟减小,Al-F络合态的氟增多,且随时间延长,溶出浓度均降低.反应开始的前1h,Al-F络合物主要以AlF3为主,占氟溶出总量的90%以上;至7h时,AlF+2的溶出量逐渐增大,并逐渐超过AlF3.低pH的柠檬酸促进土壤游离态氟和总氟的溶出,有利于络合态氟的形成,但对Al-F络合物的形态转化没有显著影响.     

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation

● A CNT filter enabled effective KMnO₄ activation via facilitated electron transfer. ● Ultra-fast degradation of micropollutants were achieved in KMnO₄/CNT system. ● CNT mediated electron transfer process from electron-rich molecules to KMnO₄. ● Electron transfer dominated organic degradation. Numerous reagents have been proposed as electron sacrificers to induce the decomposition of permanganate (KMnO₄) by producing highly reactive Mn species for micropollutants degradation. However, this strategy can lead to low KMnO₄ utilization efficiency due to limitations associated with poor mass transport and high energy consumption. In the present study, we rationally designed a catalytic carbon nanotube (CNT) membrane for KMnO₄ activation toward enhanced degradation of micropollutants. The proposed flow-through system outperformed conventional batch reactor owing to the improved mass transfer via convection. Under optimal conditionals, a > 70% removal (equivalent to an oxidation flux of 2.43 mmol/(h·m²)) of 80 μmol/L sulfamethoxazole (SMX) solution can be achieved at single-pass mode. The experimental analysis and DFT studies verified that CNT could mediate direct electron transfer from organic molecules to KMnO₄, resulting in a high utilization efficiency of KMnO₄. Furthermore, the KMnO₄/CNT system had outstanding reusability and CNT could maintain a long-lasting reactivity, which served as a green strategy for the remediation of micropollutants in a sustainable manner. This study provides new insights into the electron transfer mechanisms and unveils the advantages of effective KMnO₄ utilization in the KMnO₄/CNT system for environmental remediation.     

混酸微波辅助萃取ICP-MS测定不同性质土壤中的重金属元素

比较了硝酸(HNO3)、硝酸-盐酸(HNO3∶HCl=3∶1)、硝酸-盐酸-双氧水(HNO3∶HCl∶H2O2=3∶1∶1)和硝酸-盐酸-高氯酸(HNO3∶HCl∶HCl O4=3∶1∶1)等4种消解液对土壤中铅(Pb)、镉(Cd)、砷(As)、铬(Cr)、镍(Ni)、铜(Cu)和锌(Zn)等7种重金属元素的萃取效率.结果表明,硝酸-盐酸-高氯酸混合液的萃取效果最好,硝酸-盐酸混合液次之.通过对6种土壤标准物质的分析发现,除了Cr之外,其他重金属元素在土壤中的混酸微波可提取态含量与总含量接近.土壤中的Cr有一部分是以铬铁矿的形式存在,在环境中相对较为稳定,采用混酸微波可提取态的Cr来评估其对环境的危害能够获得更加准确的结果.重金属与土壤的结合强弱与成土母质相关,冲积母质的土壤中Pb、Zn和Cu的结合较强,萃取相对较难,Cd、Ni和As与土壤的结合强弱则与成土母质关系不大.采用最优的消解液萃取矿区河流底泥和土壤中的重金属,ICP-MS分析结果表明,底泥中重金属含量较高,应为尾砂冲积而成,矿区周边的土壤也受到不同程度重金属的污染.     

EDTA和柠檬酸对污染土壤中Cd、Ni活化的影响

以新乡市蓄电池厂周围的Cd、Ni污染土壤为研究对象,研究了不同浓度的EDTA、柠檬酸对Cd、Ni活化的影响。结果表明:在供试污染土壤中,Cd、Ni的活化量随着EDTA、柠檬酸浓度的增大而增大,EDTA对Cd、Ni的活化效果大于柠檬酸。在浓度为10.0mmol/L时,EDTA和柠檬酸对Cd、Ni的活化量都达到最大。EDTA和柠檬酸对Cd、Ni活化速度特性不同,EDTA对土壤Cd的活化速率大于柠檬酸,EDTA对土壤Ni的活化速率略大于柠檬酸。供试污染土壤中Ni不易被活化。     

阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）对磷钨酸(PW12)光催化还原降解偶氮染料直接耐晒黑G的影响

以磷钨酸H3PW12O4（PW12）为光催化剂,异丙醇（IS）作为电子给体,研究阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）对PW12光催化还原降解直接耐晒黑G（DB19）的影响.考察了CTAB浓度、pH值、DB19初始浓度等因素对反应的影响,并采用一级反应动力学对反应过程进行分析.结果表明CTAB增强了PW12对直接耐晒黑G的还原脱色作用,CTAB浓度增加,DB19的光催化脱色速率提高.PW12用量对DB19还原脱色的影响程度和趋势与溶液中CTAB浓度有关,当CTAB浓度为0.10 mmol.L-1时,DB19的脱色速率随PW12用量的增加而增加;CTAB浓度为0.05 mmol.L-1,PW12用量为200 mg.L-1时DB19的脱色速率最快,继续增加反而降低.DB19还原脱色速率随其初始浓度升高而降低.另外,通过循环伏安法和暗反应明确还原态杂多蓝对染料的还原脱色作用,并借助UV-Vis光谱研究DB19、PW12、CTAB之间的相互作用,探索CTAB对PW12/IS光催化还原降解DB19的作用机理.该研究结果表明阳离子表面活性剂CTAB能够增强偶氮染料废水的PW12催化还原脱色处理.