The formation of dithionate during the iron(III)-catalysed autoxidation of sulfur(IV)-oxides

The iron(III)-catalyzed autoxidation of sulfur(IV)-oxides results in the formation of two different oxidation products of sulfur(IV): dithionate, S₂O₆²⁻, and sulfate, SO₄²⁻. The yield of these reaction products depends on the experimental conditions. Under the studied conditions ([Fe(III)] : [SIV)] = 1:10, pH = 2–4) dithionate is the minor reaction product. The formation of dithionate is influenced by the initial pH but not by the initial O₂ concentration. The presence of CO²⁺, Mn²⁺, and Ni²⁺ have no influence on the yield of dithionate, whereas in the presence of Cr³⁺ less and, in the presence of Cu²⁺, no dithionate is formed.     

MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺,研制了将MBR和A2/O工艺相结合的新型MB(A2/O)反应器。研究了MB(A2/O)反应器处理城市污水厌氧富磷上清液的化学除磷,并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液,采用含20% Ca(OH)2的工业石灰与P的最佳投加质量比为22.5;纯Ca(OH)2与P的最佳投加质量比为5.6（摩尔比为2.5）;FeSO4·7H2O与P的最佳投加质量比为10.7（Fe2＋与P的摩尔比为1.3）;Al2(SO4)3·12H2O与P的最佳投加质量比为12（Al3＋与P的摩尔比为1.3）时,均可使出水TP稳定在0.3 mg/L以下;以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺,研制了将MBR和A²/O工艺相结合的新型MB(A²/O)反应器。研究了MB(A²/O)反应器处理城市污水厌氧富磷上清液的化学除磷,并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液,采用含20% Ca(OH)₂的工业石灰与P的最佳投加质量比为22.5;纯Ca(OH)₂与P的最佳投加质量比为5.6（摩尔比为2.5）;FeSO₄·7H₂O与P的最佳投加质量比为10.7（Fe^2＋与P的摩尔比为1.3）;Al₂(SO₄)₃·12H₂O与P的最佳投加质量比为12（Al^3＋与P的摩尔比为1.3）时,均可使出水TP稳定在0.3 mg/L以下;以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

Effect of ultrasonication and Fenton oxidation on biodegradation of bis(2-ethylhexyl) phthalate (DEHP) in wastewater sludge

The presence of bis(2-ethylhexyl) phthalate (DEHP) and its metabolites, i.e. 2-ethylhexanol, 2-ethylhexanal, and 2-ethylhexanoic acid in wastewater sludge (WWS) were investigated during aerobic digestion and Bacillus thuringiensis (Bt)-based fermentation of WWS. Ultrasonication and Fenton oxidation pre-treatment was applied to improve biodegradability of WWS and bioavailability of the target compounds for digestion and fermentation. DEHP and 2-ethylhexanoic acid were observed at higher concentration, meanwhile 2-ethylhexanol and 2-ethylhexanal were observed at lower concentration in WWS. After 20-day aerobic digestion, DEHP removal was 72%, 89%, and 85%, and 2-ethylhexanoic acid removal was 71%, 84%, 79%, respectively for raw, ultrasonicated, and Fenton-oxidized sludges. Bt was found to degrade DEHP, leading to DEHP removal of 21%, 40%, and 30%, respectively for raw, ultrasonicated, and Fenton-oxidized sludges in the fermentation. The results suggested that aerobic stabilization and Bt-based fermentation can remove the phthalates, and pre-treatment of WWS was also effective in improvement of DEHP biodegradation. Hence, Bt-based biopesticide production from WWS can be applied safely when taking into consideration the phthalate contaminants.     

铁炭微电解-MAP沉淀法联合预处理垃圾渗滤液

采用铁炭微电解-磷酸氨镁(MAP)沉淀法对垃圾渗滤液进行预处理,实验结果表明,铁炭比为5∶1,pH值为3,反应时间为3 h时,铁炭微电解的COD的去除率为47.5%;在投加药剂n(Mg2+)∶n(PO43-)∶n(NH4+)为1.4∶1∶1,pH值为9,反应时间为1 h的条件下,垃圾渗滤液氨氮去除率达到79.7%。     

磷酸铵镁碱促(Mg(OH)2)热解产物氨氮去除性能

磷酸铵镁热解循环技术可以有效降低磷酸铵镁结晶技术的药剂费用。同时,在磷酸铵镁热解过程中添加Mg(OH)2碱促媒介,能阻止磷酸氢镁向焦磷酸镁的转化,并降低热解产物氨氮去除过程中上清液磷酸盐的残留。在Mg(OH)2:NH4+摩尔比为1:1,热解温度为110℃条件下,热解产物沉氨效率接近84%,上清液磷酸盐残留量为0.02 mg/L。     

黄钠铁矾渣制备透明氧化铁黄的研究

研究了以黄钠铁矾渣为原料,采用滴加法制备透明铁黄的工艺条件,讨论了亚铁浓度、温度、通气量、搅拌速度及添加剂用量等因素对铁黄制备的影响.用XRD和TEM对产品进行表征.结果表明,铁黄粒子呈针状;长轴为95～125 nm,短轴为18～25 nm;无团聚现象,单分散性好.     

飞灰-氢氧化钙/聚苯硫醚(PPS)滤料对烟气中单质汞的脱除

在汞固定床实验台上进行了飞灰-氢氧化钙和PPS滤料负载飞灰-氢氧化钙吸附单质汞,以及不同温度、气体成分对滤料负载吸附剂脱除汞影响的实验研究。实验结果表明,质量配比为2:1的飞灰-Ca(OH)2吸附剂对Hg0的脱除效果最好,最高可达到34.5%左右,比纯飞灰条件下的脱除效率提高了近10%。120℃条件下,PPS滤料负载飞灰-Ca(OH)2吸附剂对汞的脱除率最高达72%,远高于滤纸薄膜上吸附剂的脱除率。随着温度升高,PPS滤料负载吸附剂的脱除效率降低。HCl、SO2和NO对PPS负载吸附剂脱除汞表现出不同程度的促进作用,HCl具有很强的促进作用,少量HCl足以大幅度提高脱除效果,SO2有一定的促进作用,NO的促进效果并不明显。     

微波活化对Ca(OH)2孔隙结构及脱氯性能的影响

采用微波炉对一定质量的氢氧化钙样品进行活化,利用压汞仪考察了不同微波活化时间及脱氯反应前后的Ca(OH)2总比孔表面积、分段比表面积和孔径分布的变化,并在脱氯实验台上对脱氯效率进行实际测试。结果表明,微波活化存在一个最佳时间,在此时间内样品比孔表面积增大50%左右,而超过这一时间样品比表面积回复性减小;微波活化主要通过增加3～20 nm孔径段的微孔为样品提供更大比表面积;这些新增加的微孔在脱氯反应过程中被完全利用或消耗; 最佳活化时间下的微波活化使Ca(OH)2在较低Ca/Cl摩尔比下获得更大脱氯效率,Ca/Cl摩尔比=4.1时,脱氯效率增加了20%。     

分子印迹型TiO2的制备及其对邻苯二甲酸二(2-乙基)己酯的光催化性能

以邻苯二甲酸二（2-乙基）己酯为模板分子、甲基丙烯酸为功能单体和乙二醇二甲基丙烯酸酯为交联剂,在TiO2表面合成DEHP分子印迹聚合物,制备了分子印迹型TiO2（MIP-TiO2）,优化了制备工艺条件。利用傅里叶红外光谱（FI-IR）和X-射线衍射（XRD）对MIP-TiO2进行表征,并考察了MIP-TiO2对DEHP的光催化降解性能。结果表明,MIP-TiO2的最佳制备工艺条件为模板分子、单体、交联剂和TiO2的摩尔比为1：4：10：1.875,反应温度为60 ℃;聚合时间为18 h。MIP-TiO2仍保持了和TiO2一样的锐钛矿型结构,对DEHP 的光催化效果明显高于TiO2,对浓度为5 mg·L-1的DEHP的光催化降解效率可达88.15%。     

改良型A2/O-MBR工艺的反硝化除磷性能研究简

重点考察了一种改良型膜生物反应器（A²/O-MBR）的脱氮除磷性能。该工艺主要特点在于对膜池硝化回流液进行了固液分离,并将上清液和浓缩污泥分别回流至缺氧池和厌氧池,这种改进提高了系统对氮、磷的同步去除效率。实验结果表明,在水力停留时间（HRT）为12 h,污泥龄（SRT）为30 d,混合液回流比为200%的运行条件下,进水COD、NH₄⁺-N、TN和TP平均浓度分别为（225±38）、（24.8±3.9）、（26.7±2.9）和（2.90±0.53）mg/L时,增加膜池硝化回流液固液分离装置前后,系统对COD和NH₄⁺-N的去除都维持在较高水平,而系统对TN和TP的去除效果显著提高,出水TN和TP平均浓度分别由（14.9±3.3）mg/L和（1.95±0.72）mg/L下降到（9.4± 1.9）mg/L和（0.91±0.38）mg/L,表明增加膜池硝化回流液固液分离装置显著改善了A²/O-MBR系统的脱氮除磷效果。反硝化除磷活性实验结果进一步表明,改进后系统中反硝化除磷活性占总除磷活性的比例由51.5%上升至61.7%,说明增加膜池硝化回流液固液分离装置强化了系统的反硝化除磷性能。     

Iron-catalyzed oxidation of s(IV) species by oxygen in aqueous solution: Influence of pH on the redox cycling of iron

Redox cycling of Fe(II)/Fe(III) during the catalyzed aqueous S(IV) oxidation by dissolved oxygen in the presence of Fe(II) and/or Fe(III) at an initial pH_i of 4.4, often observed in atmospheric waters, was studied in detail. It has been found that the reaction rate is not considerably affected by the oxidation state of iron at the start of the reaction. An equilibrium between Fe(II) and Fe(III) was established a few minutes after the start of the reaction, regardless of the oxidation state of iron at the beginning of the experiment. The prevailing oxidation state of iron in a particular phase of the reaction depends on the concentration of S(IV) in the reaction solution. It has been found that the formation of polymerized hydroxo Fe(III) species is also included in the mechanism of the Fe-catalyzed oxidation of S(IV). The formation of these species was confirmed by the on-line measurement of Fe(II) and Fe_reac. The results also clearly demonstrate that the pH_i of the solution is a major factor, controlling the concentration of Fe(III) ions, the form of S(IV) species, and consequently the reaction rate of S(IV) oxidation by oxygen.     

Surfactant effect on persistence of oxadiazolyl 3(2H)-pyridazinones against Pseudaletia separata walker

The photodynamic decomposition of two new insect-growth inhibitors (IGRs), 2-tert-butyl-5-[5′-aryl-2′-(1′,3′,4′-oxadiazolyl)methoxy]-3(2H)-pyridazinones (OPB) and its 4-chloro substituted derivative (OPC), and effect of surfactants on persistence of their bioactivity were taken into investigation. Both chemicals were significantly induced to photolysis by ultraviolet light at 365 nm wavelength and their inhibitory activities against Pseudaletia separata larvae decreased with the increasing irradiation time. However, irradiation at 254 nm wavelength didn't cause their photodegradation. Triton X-100 and Succinic-sulfonie acidic sodium but not Tween 60 possessed strong capability to slow down the decomposition and obviously prolonged the half life of OPC in laboratory and field whilst effects of the three surfactants almost did not preserve the inhibitory activity of OPB. Data suggested that electron-withdrawing halogen (?Cl) on the π electron system in planar benzene-oxadialyl structures might reduce the efficiency of OPC on ultraviolet (UV) photoabsorption, and its hydrophobic interaction with the surfactants might be beneficial for forming stable micellar solubilization, thus sustaining the chemical's bioactivity.     

Organochlorines, brominated flame retardants and mercury levels in six seabird species from the Gulf of St. Lawrence (Canada): Relationships with feeding ecology, migration and molt

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (ΣPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (ΣCPs), the sum of brominated flame retardants (ΣBFRs) and finally total Hg (THg). ΣPCBs, ΣCPs and ΣBFRs increased with trophic level, whereas THg did not. Only ΣBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.     

地下水化学类型对硫系还原剂去除Cr (VI)的影响

为研究铬污染地下水化学类型对硫系还原剂除铬的影响,采用批实验的方式,分别比较了3种还原剂焦亚硫酸钠（Na2S2O5）、连二亚硫酸钠（Na2S2O4）、多硫化钙（CaSx）对SO4-Na型、SO4-Ca型、Cl-Na型和HCO3-Ca型4种地下水中去除Cr（VI）的效果。结果表明,在20℃有氧条件下,4种地下水环境中还原剂的除铬能力受到了不同程度的抑制,其中HCO3-Ca型地下水中的抑制作用最大。但当Na2S2O5、Na2S2O4、CaSx投加量分别为理论投加量的30.8、21.7和2.4倍时,4种地下水中Cr（VI）的去除率均大于90%。Na2S2O5投加量与水中HCO3-含量的摩尔比大于0.5时,Cr（VI）才可能被还原去除;Na2S2O4对Cr（VI）的去除率由高到低排序是：SO4-Na型 > Cl-Na型 > SO4-Ca型 > HCO3-Ca型;CaSx的除铬效果在不同地下水化学类型中的差异最小。地下水的HCO3-含量越高,缓冲能力越强,抑制作用越明显,所需还原剂投加量越多。     

NiFe2O4/ZnAl-LDH吸附去除水中Cr(VI)

采用共沉淀法合成磁性复合材料NiFe2O4/ZnAl-LDH,通过静态吸附试验考察复合材料去除水中Cr（VI）的性能,系统地研究了溶液初始pH值、吸附剂投加量、吸附时间和温度等因素对Cr（VI）去除效果的影响。结果表明,当溶液初始pH值为2、初始Cr（VI）浓度为50 mg·L-1、吸附剂投加量为4 g·L-1时,吸附过程在240 min内达到平衡,此时Cr（VI）的去除率为89.5%。动力学和吸附等温式的研究表明：NiFe2O4/ZnAl-LDH吸附Cr（VI）的过程符合准二级动力学和Langmuir等温吸附模型。热力学参数表明该吸附过程为自发、放热的反应过程,低温有利于吸附剂对Cr（VI）的吸附。吸附剂经4次再生后对Cr（VI）仍有83.1%的去除率,且其在外加磁场的作用下能快速与水溶液分离,因此NiFe2O4/ZnAl-LDH可作为去除水中Cr（VI）的良好吸附剂。     

Derivation of aquatic predicted no-effect concentration (PNEC) for 2,4-dichlorophenol: comparing native species data with non-native species data

2,4-Dichlorophenol (2,4-DCP) is known as an important chemical intermediate and an environmental endocrine disruptor. There is no paper dealing with the predicted no-effect concentration (PNEC) of 2,4-DCP, mainly due to shortage of chronic and site-specific toxicity data. In the present study, toxicity data was obtained from the tests using six Chinese native aquatic species. The HC₅ (hazardous concentration for 5% of species) was derived based on the constructed species sensitivity distribution (SSD), which was compared with that derived from literature toxicity data of non-native species. For invertebrates, the survival no-observed effect concentrations (NOECs) were 0.05 and 1.00 mg L⁻¹ for Macrobrachium superbum and Corbicula fluminea, respectively. NOECs based on fishes’ growth were 0.10, 0.20 and 0.40 mg L⁻¹ for Mylopharyngodon piceus, Plagiognathops microlepis and Erythroculter ilishaeformis, respectively. For aquatic plant Soirodela polyrhiza, NOEC based on concentration of chlorophyll was 1.00 mg L⁻¹. A final PNEC calculated using the SSD approach with a 50% certainty based on different taxa ranged between 0.008 and 0.045 mg L⁻¹. There is no significant difference between HC₅ derived from native and that from non-native taxa.     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

荧光光纤传感器测定废水中邻硝基苯酚

将２－（４－二苯基）－６－苯基苯并恶唑包埋在增塑的ＰＶＣ膜中,基于邻硝基苯酚对ＰＢＢＯ荧光的猝灭,研制了一种邻硝基苯酚荧光光纤传感器。该传感器对邻硝基苯酚的响应具有良好的可逆性和重现性,响应时间小于５０ｓ,在１．２＊１０＾－４－２．０＊１０－６ｍｏｌ／Ｌ邻硝基苯酚浓度范围内具有好的线性关系。环境水中可能存在的常见阳离子、阴离子、酚、硝基化合物对邻硝基苯酚的测定不产生干扰,将传感器用于废水中的邻硝基