Role of interfacial electron transfer reactions on sulfamethoxazole degradation by reduced nontronite activating H2O2

It has been documented that organic contaminants can be degraded by hydroxyl radicals ( • OH) produced by the activation of H₂ O₂ by Fe(II)-bearing clay. However, the interfacial electron transfer reactions between structural Fe(II) and H 2 O 2 for • OH generation and its effects on contaminant remediation are unclear. In this study, we first investigated the relation between • OH generation sites and sulfamethoxazole (SMX) degradation by activating H₂O₂ using nontronite with different reduction extents. SMX (5.2–16.9 μmol/L) degradation first increased and then decreased with an increase in the reduction extent of nontronite from 22% to 62%, while the • OH production increased continually. Passivization treatment of edge sites and structural variation results revealed that interfacial electron transfer reactions between Fe(II) and H 2 O 2 occur at both the edge and basal plane. The enhancement on basal plane interfacial electron transfer reactions in a high reduction extent rNAu-2 leads to the enhancement on utilization efficiencies of structural Fe(II) and H 2 O 2 for • OH generation.However, the • OH produced at the basal planes is less efficient in oxidizing SMX than that of at edge sites. Oxidation of SMX could be sustainable in the H 2 O 2 /rNAu-2 system through chemically reduction. The results of this study show the importance role of • OH generation sites on antibiotic degradation and provide guidance and potential strategies for antibiotic degradation by Fe(II)-bearing clay minerals in H 2 O 2 -based treatments.     

Surface characterization of metal oxides-supported activated carbon fiber catalysts for simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide

The sol–gel method was used to synthesize a series of metal oxides-supported activated carbon fiber (ACF) and the simultaneous catalytic hydrolysis activity of carbonyl sulfide (COS) and carbon disulfide (CS₂) at relatively low temperatures of 60°C was tested. The effects of preparation conditions on the catalyst properties were investigated, including the kinds and amount of metal oxides and calcination temperatures. The activity tests indicated that catalysts with 5 wt.% Ni after calcining at 400°C (Ni(5)/ACF(400)) had the best performance for the simultaneous catalytic hydrolysis of COS and CS₂. The surface and structure properties of prepared ACF were characterized by scanning electron microscope-energy disperse spectroscopy (SEM-EDS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), carbon dioxide-temperature programmed desorption (CO₂-TPD) and diffuse reflectance Fourier transform infrared reflection (DRFTIR). And the metal cation defects were researched by electron paramagnetic resonance (EPR) method. The characterization results showed that the supporting of Ni on the ACF made the ACF catalyst show alkaline and increased the specific surface area and the number of micropores, then improved catalytic hydrolysis activity. The DRFTIR results revealed that -OH species could facilitate the hydrolysis of COS and CS₂; -COO and -C–O species could facilitate the oxidation of catalytic hydrolysate H₂S. And the EPR results showed that high calcination temperature conditions provide more active reaction center for the COS and CS₂ adsorption.     

氨氮和硫酸盐对谷氨酸厌氧生物降解性能的抑制及机理

采用连续运行1119d的上流式厌氧污泥床（UASB）反应器,研究了最佳有机负荷条件下氨氮和硫酸盐对模拟废水中谷氨酸降解性能的抑制作用.结果表明,有机负荷为8.0g COD/（L·d）时,COD去除率达到最高值为（97.94±0.28）%.逐步提高进水氨氮浓度,起初对谷氨酸降解性能的影响不大;但升到2000mg/L时COD去除率和甲烷产率明显降低,继续升至4000mg/L时即达到半抑制状态.逐步提高进水硫酸盐浓度至4000mg/L,甲烷产率和溶液中游离硫化氢（FS）浓度分别呈现一直下降和升高趋势,但COD去除率均能维持在90%以上.进水中的氨氮和硫酸盐分别因离解平衡和生物还原作用形成游离氨（FAN）和FS,进而抑制了产甲烷菌的活性;前者因FAN扩散到细胞内部破坏质子平衡从而过多消耗ATP,后者还因硫酸盐还原菌的增殖存在底物竞争抑制作用.     

Town-scale microbial sewer community and H2S emissions response to common chemical and biological dosing treatments

Controlling hydrogen sulfide (H₂S) odors and emissions using a single, effective treatment across a town-scale sewer network is a challenge faced by many water utilities. Implementation of a sewer diversion provided the opportunity to compare the effectiveness of magnesium hydroxide (Mg(OH)₂) and two biological dosing compounds (Bioproducts A and B), with different modes of action (MOA), in a field-test across a large sewer network. Mg(OH)₂ increases sewer pH allowing suppression of H₂S release into the sewer environment while Bioproduct A acts to disrupt microbial communication through quorum sensing (QS), reducing biofilm integrity. Bioproduct B reduces H₂S odors by scouring the sewer of fats, oils and grease (FOGs), which provide adhesion points for the microbial biofilm. Results revealed that only Mg(OH)₂ altered the microbial community structure and reduced H₂S emissions in a live sewer system, whilst Bioproducts A and B did not reduce H₂S emissions or have an observable effect on the composition of the microbial community at the dosed site. Study results recommend in situ testing of dosing treatments before implementation across an operational system.     

氧化环境中FeS修复重金属的稳定性变化与机制

硫化亚铁(FeS)是良好的重金属修复剂,但它对氧化环境敏感.当环境氧气浓度升高时,FeS对重金属的固定效果可能发生改变.本研究考察了氧化环境中FeS与重铬酸根、铅和镉离子的反应规律和结合机制变化.结果表明,环境氧气浓度升高可促进Fe~(2+)的释放,且增加FeS表面S(-II)氧化态的比例(与Pb~(2+)反应:从24%增加到44%,与Cd~(2+)反应:从60%增加到78%).延长反应时间至30 d,虽然PbS和CdS结晶度提高,但两者表面出现Pb—O和Cd—O氧化形态,预示着重金属再释放的风险.有氧干燥条件下FeS表面矿物相转变为纤铁矿,对Cr(VI)的还原能力大幅下降.与未干燥FeS(FeS-Cr-3h)相比,当有氧干燥的FeS与Cr(VI)反应时,总铬的去除量下降约96%(由约100 mg·g~(-1)降至(3.74±1.12) mg·g~(-1)),Cr(VI)去除量下降约57%(由约100 mg·g~(-1)降至(43.28±0.46) mg·g~(-1)).FeS及重金属硫化物的氧化显然不利于重金属的长期稳定.如何延缓或抑制FeS与重金属硫化物的氧化因此成为未来研究需回答的问题.     

荧光灯管芯柱玻璃中金属铅的机械化学硫化

以硫化钠为硫化剂,机械化学硫化荧光灯管芯柱玻璃中金属铅,实现金属铅向硫化铅快速转化.通过单因素实验,考察了不同机械化学硫化条件,即球磨时间、球磨转速和球料比对硫化率的影响,并通过XRD、SEM和粒度对硫化产物进行表征.结果表明,硫化率随球磨时间和球磨转速的增大而增大,随球料比的增大先增大后减小,当球磨转速为750r/min、球磨时间为120min、球料比为50：1g/g时,荧光灯管芯柱玻璃中金属铅的硫化率可达96.18%.XRD结果表明,荧光灯管芯柱玻璃中金属铅的机械化学硫化产物为PbS、SEM和粒度结果表明,荧光灯管芯柱玻璃的粒径随球磨转速和球磨时间的增加而减小.     

富硫沉积生境中微生物群落的垂直分布特征

为探讨富硫沉积环境中特定微生物类群对硫循环的贡献,人工建立富含硫酸盐的模型,对模型中各种环境化学参数进行监测,并采用不依赖于培养的微生物分子生态学技术对微生物群落垂向分布特征进行解析.结果表明,以沉积物-水界面为分界线,上层水相为好氧环境,硫化物浓度较底;而沉积物相中硫化物浓度较高,为厌氧生境.微生物群落分布与环境特征具有很好的吻合性,沉积物相中微生物群落相似性较高,多样性相对较低,而水相中微生物多样性较高,且与沉积物中微生物分离距离较大.在水-沉积物垂向剖面中,细菌域中的变形菌门(Protebacteria)(丰度为7.6%~32.8%)、绿弯菌门(Chloroflexi)(13.6%~22.3%)以及古菌域中的广古菌门(Euryarchaeota)(19.3%~29.2%)是微生物群落中的绝对优势类群.在该生境中,存在微生物主导的硫循环过程,在厌氧沉积物表层,δ变形菌纲(Deltaprotebacteria)中的硫酸盐还原细菌还原硫酸盐产生硫化物,同时降解有机质.硫化物向上层扩散时,被Thiobacillus、Acidithiobacillus和Halothiobacillus等属的硫氧化微生物氧化为单质硫,并进一步氧化为硫酸盐,在硫循环过程中有机质被逐渐降解.特定微生物种群的富集需要在不同的环境因素,多种微生物共同参与硫循环过程,完成有机质降解.     

Persistence of fensulfothion in a sandy‐loam soil and uptake by rutabagas,carrots and radishes using microplots

Abstract

Field microplots were treated with 141 and 282 ppm fensulfothion and 37.1 and 74.2 ppm fensulfothion sulfone. These concentrations are equivalent to field treatment rates of 8.48 and 16.96 kg Al/ha, fensulfothion, and 2.23 and 4.47 kg Al/ha, fensulfothion sulfone, respectively, for banded application (10 cm wide, rows 80 cm apart). The half‐lives in a sandy loam soil were 30–39 and 14–23 days, respectively. Fensulfothion sulfone and sulfide were the main derivatives found in fensulfothion treated soil.

The maximum levels of these derivatives were 21.22 and 22.95 ppm, respectively for the 8.48 kg/ha treatment and 33.90 and 42.45 ppm, respectively, for the higher treatment, which occurred between 30–60 days.

Carrots appeared to take up more fensulfothion from soil than rutabagas or radishes. The residue levels at harvest decreased in the order carrot peel > pulp > rutabagas root > peel > pulp. Residue levels of fensulfothion and sulfone in radishes were similar to those found in rutabagas. The ratio sulfoxide/sulfone in rutabagas ranged from 0.4–1.5 and in carrots from 1.7–7.6. This phenomenon is thought to be due to oxidative enzyme systems present in rutabagas. Dimethyl phosphorothioic acid, but not dimethyl phosphoric acid was detected (max. 1.33 ppm) in some rutabagas samples but not in carrots.     

常温下铁的硫化产物自燃性

含硫油品储运过程中H2S腐蚀产物是常温下硫铁化合物的主要来源,以H2S与铁粉反应制备的硫铁化合物来模拟设备内H2S的腐蚀产物,利用自然氧化的方法测定了硫化反应产物的一次氧化升温和二次氧化升温,考察了铁粉含水量对硫化反应及硫化反应产物自燃性的影响,采用XRD和SEM手段对硫化反应产物进行了表征。结果表明:H2S与铁粉的硫化反应产物为FeS,呈微小颗粒状,覆盖在铁粉表面;硫化反应产物具有自燃性,一次氧化升温最高达到87℃;未被完全氧化的硫化反应产物密封放置一段时间后自燃性明显增加,其二次氧化升温速率最高超过39℃/min;铁粉中含有适量的水可以增加硫化反应速率,提高硫化反应产物的自燃性。     

连续流动分析法测定水中硫化物的显色剂配制方法研究

针对连续流动分析法测定水中硫化物方法中显色剂N,N-二甲基-1,4苯二胺二盐酸盐保质期短的问题,研究了不同体积比盐酸或硫酸介质对延长显色剂保质期的影响,确定了延长保质期的试剂配制方法,并对该方法的适用性进行了检验.结果显示,体积比10％硫酸介质的显色剂优于盐酸介质显色剂,可以存放一周.使用此显色剂进行硫化物分析检出限为0.003 mg/L,线性范围0.000 mg/L ～2.00 mg/L,平行测定相对偏差0.0％ ～11.8％,加标回收率82.0％～102％,可以满足环境样品分析需求.