Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)₂. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (< 10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L–0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

中国硫酸盐气溶胶直接辐射效应数值模拟

硫酸盐气溶胶对地球系统能量收支平衡和全球气候变化有重要影响.本研究基于中国2007年二氧化硫排放清单,应用Can METOP、OPAC和SBDART模型,对中国硫酸盐气溶胶直接辐射效应及其空间分布和时间变化进行分析.结果表明,2007年中国硫酸盐气溶胶直接辐射效应全年波动范围在-9.1~0.0008 W·m~(-2)之间,全国年均值为-1.372 W·m~(-2),低于全球均值(-0.35 W·m~(-2)),其中华东地区最强为-5.017 W·m~(-2),西北地区最弱仅为-0.22 W·m~(-2),该空间分布主要受SO_2排放的空间差异及西风导致的向东溢出效应影响.同时,除华南之外的绝大多数地区夏季辐射效应最强、冬季最弱,这主要由SO_2向硫酸盐的转化率及相对湿度的季节差异决定.本研究有助于了解中国硫酸盐气溶胶及其气候效应的时空差异,对评估硫酸盐气溶胶的气候效应有重要意义.     

CMC-nZVI对高硫矿山土壤中铜的固定效果及机理

纳米零价铁(Nanoscale zero-valent iron,n ZVI)因具有较大比表面积和较强还原能力,常被用于原位修复变价重金属污染土壤,而对其应用于高硫富铜矿山土壤的修复及机理研究却鲜见报道.本研究以羧甲基纤维素-纳米零价铁(CMC-n ZVI)为供试材料,以广东省大宝山矿区高硫富铜土壤为供试土壤,按水土比1 g∶5 m L将CMC-n ZVI与矿山土壤混合均匀,通过毒性淋溶提取、重金属形态和酸可挥发性硫化物提取等实验,探究了CMC-n ZVI对矿山土壤中Cu的固定效果及机制.结果表明:(1)CMC-n ZVI对高硫土壤中的Cu具有极好的固定效果,毒性淋溶提取实验结果表明,n ZVI处理土壤中Cu的浸出浓度低于15 mg·kg-1,达到安全标准;(2)n ZVI可促进厌氧微生物的活性,促进土壤中大量硫酸盐被还原,因此Cu可能被Fe S、Fe S2吸附或直接生成硫化物沉淀,最终固定于土壤中;(3)新生成的无定形或微晶型次级铁矿物易通过吸附或共沉淀将游离的Cu(II)固定.     

含硫酸盐高浓度有机废水酸化规律研究

以糖蜜酒精废液为材料,通过梯度稀释和序批式酸化实验,研究了含硫酸盐高浓度有机废水的一般酸化规律.结果表明,糖质废水酸化的挥发酸(VFA)组分以乙酸和丁酸为主要形式;VFA对硫酸盐还原的完全抑制浓度介于23553～35241mg/L(以COD计)之间;VFA对产酸过程的反馈抑制浓度介于35241～37109mg/L之间;不同稀释度废水酸化后的可生化性提高幅度平均为10%.     

Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system

Selective catalytic reduction (SCR) denitration may increase the emission of NH₄⁺ and NH₃. The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization (WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system. The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH₄⁺ will generate new ammonium-containing particles and gaseous ammonia. The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation. Therefore, even if the concentration of NH₄⁺ in the desulfurization slurry is quite low, a high level of NH₄⁺ was still contained in the fine particles at the outlet of the scrubber. When the accumulated NH₄⁺ in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH₃ to NH₄⁺ and increased the additional emission of primary NH₄⁺ aerosols. With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH₄⁺ emitted from entrainment and evaporation of the desulfurization slurry decreased. In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH₄⁺ concentration and pH values of the slurry.     

南京冬夏硫酸盐和硝酸盐对黑碳混合态的影响

采用单颗粒黑碳光度计（SP2）结合MARGA在线分析仪对南京地区冬季和夏季黑碳（BC）的质量浓度,以及硫酸盐,硝酸盐对其混合状态的影响进行了研究.结果表明,冬季和夏季南京地区BC质量浓度分别在1.01~14.5μg/m³和0.20~3.81μg/m³之间,均值分别为（4.39±2.66）μg/m³和（1.67±0.76）μg/m³,均呈现早晚高值的双峰型日变化特征.运用相对包裹层厚度D_p/D_c表示BC混合状态,冬季和夏季D_p/D_c分别在1.39~2.34和1.03~1.45之间,均值分别（1.81±0.21）和（1.24±0.08）,D_p/D_c日变化特征与BC相反,冬季D_p/D_c日变化幅度较大.冬季D_p/D_c与SO₄^2-和NO₃^-的相关性较好,D_p/D_c与NO₃^-的相关性高于其与SO₄^2-的相关性,夏季则相反.冬季清洁时期BC以本地源排放为主,其混合状态受硫酸盐和硝酸盐影响较高,冬季重污染时期,受排放源以及区域传输的影响,D_p/D_c与SO₄^2-和NO₃^-的相关性较低.     

聚离子液体刷接枝改性PVDF膜及其对药物硫酸氢氯吡咯雷分离性能研究

以聚偏氟乙烯(PVDF)超滤膜为底膜,通过浸渍法使多巴胺(DOPA)在膜表面形成聚多巴胺(PDOPA)层,然后由化学反应固定溴代卤化物,并通过原子转移自由基聚合(ATRP)反应在膜表面接枝聚离子液体刷(PBIVm-Br),以制备聚离子液体刷改性PVDF膜,即PVDF-g-PBIVm-Br膜.结果表明,改性PVDF膜的接触角下降至60°以下且显示出良好的荷正电性.改性膜的药物通量和截留率均大于未改性PVDF膜,分离10 mg·L~(-1)的硫酸氢氯吡咯雷时,改性膜(M4)的药物通量可达27.62 L·m~(-2)·h~(-1),截留率为89.03%,通量恢复率为95.32%.经过60 h分离实验后,膜M4对硫酸氢氯吡咯雷溶液的分离通量维持在18.05 L·m~(-2)·h~(-1),截留率从89.03%上升到92.19%.以上结果表明,聚离子液体刷改性膜在荷正电有机污染物的分离方面具有一定的应用前景.     

外源硫酸盐对武汉南湖表层沉积物磷形态的作用

采用室内模拟实验,选取武汉市南湖表层沉积物及相应上覆水,研究了硫酸盐的输入对沉积物磷形态的影响.结果表明,硫酸盐输入水体后提高了沉积物磷的迁移活性,导致上覆水中总磷(TP)、溶解性正磷酸盐(SRP)含量升高,上升幅度随硫酸盐输入量的增加而增加.硫酸盐扩散到沉积物后,先是生成酸可挥发性硫(AVS),进而转变成铬还原硫.硫酸盐输入提高了沉积物pH值,而使Eh降低.沉积物不同磷形态对外源硫酸盐的响应有所差异,二钙磷(Ca2-P)含量随输入硫酸盐浓度的增加而增加,含量最高的铁磷(Fe-P)为800mg/kg左右,占总磷的51.4%~56.6%,受硫酸盐的影响极显著(P<0.01),在沉积物中含量降低而向上覆水中释放.上覆水中溶解性铁和TP、SRP均呈显著正相关.硫酸盐对沉积物中闭蓄态铁磷(O-Fe-P)也产生显著影响(P < 0.05),总体而言是促进其释放.     

硫丹及硫丹硫酸酯的土壤降解特性

在实验室条件下研究了α-硫丹、β-硫丹及硫丹硫酸酯在东北黑壤土、江苏水稻土、江西红壤土和河南二合土4种土壤中的降解特性.结果表明,硫丹及硫丹硫酸酯降解过程可用一级动力学方程描述.4种土壤中,β-硫丹的降解半衰期(DT50)分别为39、10、14和13d;α-硫丹的DT50分别为72、56、105和42d;硫丹硫酸酯的DT50分别为39、41、53和34d,因此,硫丹硫酸酯在土壤中的持久性值得关注.α-硫丹在有机质含量丰富的土壤中降解较慢,β-硫丹在碱性土壤中降解较快.用一级动力学模型模拟的硫丹(α-硫丹+β-硫丹)和总硫丹(α-硫丹+β-硫丹+硫丹硫酸酯)降解过程的计算结果表明,硫丹的DT50为18～47d,总硫丹的DT50为48～77d.试验观察到的硫丹降解产物依次为硫丹硫酸酯、硫丹二醇、硫丹醚和硫丹羟基醚.     

Interaction of PACls with sulfate

IntroductionPolyaluminumchloride (PACl)asamainkindofinorganicpolymerflocculantsisanewhighereffectivewaterandwastewatertreatmentreagent.Basedonthetraditionallow molecularaluminum ,ithasbeendevelopedworldwidesincethe 196 0s(Tang,1994 ;1990 ;1987) .PAClistheintermediateproductofthehydrolysis polymerization ageingprocessofAl(III)undersuitableconditions.Atpresent,itisgenerallyknownthattherearemanypossiblespeciesexistintheAl(III)solution ,suchasmonomers,oligomers,Al13 [AlO4Al12 (OH) 2 4(H2 …     

外加碳源水淹条件下高硫土壤中铜的迁移转化

采用高硫低有机质酸性重金属污染土壤,通过研究外加碳源水淹条件下各层土壤中酸可挥发性硫化物(AVS)的产生以及各剖面层中Cu的总量分布、Cu在孔隙水中的浓度及存在形态的变化情况,探讨了水淹土壤中的AVS对Cu迁移转化的影响.结果表明,外加碳源水淹条件下,硫酸根被还原,产生的大量AVS可促使水相中游离活性Cu向惰性较高的硫化物结合态和残渣态转化而被固定;不同深度土壤中AVS产生情况不同,其含量由深层向浅层递增,并在顶层大量聚集,由此导致孔隙水中的Cu²⁺浓度由土壤深层向浅层递减,这种垂直浓度梯度差,趋动活性态Cu由深层向浅层的垂直迁移,在AVS大量富集的表层中形成丰富的铜硫化物沉淀,使土壤表层中惰性态铜及总量累积增加,底层活性铜及总量下降,从而使铜的生态风险和生物风险降低.     

铁元素对硫酸盐还原过程的影响及微生物群落响应

采用常规化学分析和微生物群落变性梯度凝胶电泳(DGGE)监测技术,探讨投加不同价态铁元素对硫酸盐还原过程的影响以及相应的微生物群落动态响应.结果表明,反应器启动后5d内硫酸盐去除率达到80%,在此过程中群落条带逐渐减少,但与已分离的硫酸盐还原菌(SRB)菌株一致的条带并没出现;Fe³⁺的投加极显著地改变了原有的高效群落结构,硫酸盐去除率降至20%,氧化还原电位(ORP)有所上升;而Fe²⁺和Fe0的投加未改变已经形成的顶极群落结构模式,也未显著降低硫酸盐去除率,仅硫化物的浓度变化对Fe²⁺的投加有短暂的响应.     

硫酸盐废水生物脱硫研究进展

含硫酸盐废水的污染是一个全球性的问题。生物脱硫技术处理该类废水具有投资少、成本低、去除率高,无二次污染等优点,而成为废水处理技术的前沿课题。文章简要介绍了生物脱硫技术的基本原理;描述了废水脱硫微生物种类及其影响因素;重点阐述了国内外硫酸盐废水生物脱硫工艺的沿革和最新进展,并在此基础上,提出了酸酸盐废水生物脱硫技术的发展前景。     

Groundwater arsenic removal by coagulation using ferric(Ⅲ)sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic(As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate(FS) and polyferric sulfate(PFS)performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)_2. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water( 10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure(XANES) and As k-edge extended X-ray absorption fine structure(EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As(0.9 μg/L–0.487 mg/L)than the US EPA regulatory limit(5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

Characteristics of secondary inorganic aerosol and sulfate species in size-fractionated aerosol particles in Shanghai

Sulfate, nitrate and ammonium(SNA) are the dominant species in secondary inorganic aerosol, and are considered an important factor in regional haze formation. Size-fractionated aerosol particles for a whole year were collected to study the size distribution of SNA as well as their chemical species in Shanghai. SNA mainly accumulated in fine particles and the highest average ratio of SNA to particulate matter(PM) was observed to be 47% in the fine size fraction(0.49–0.95 μm). Higher sulfur oxidation ratio and nitrogen oxidation ratio values were observed in PM of fine size less than 0.95 μm. Ion balance calculations indicated that more secondary sulfate and nitrate would be generated in PM of fine size(0.49–0.95 μm). Sulfur K-edge X-ray absorption near-edge structure(XANES) spectra of typical samples were analyzed. Results revealed that sulfur mainly existed as sulfate with a proportion(atomic basis) more than 73% in all size of PM and even higher at 90% in fine particles. Sulfate mainly existed as(NH4)2SO4 and gypsum in PM of Shanghai. Compared to non-haze days, a dramatic increase of(NH4)2SO4 content was found in fine particles on haze days only, which suggested the promoting impact of(NH4)2SO4 on haze formation. According to the result of air mass backward trajectory analysis, more(NH4)2SO4 would be generated during the periods of air mass stagnation. Based on XANES, analysis of sulfate species in size-fractionated aerosol particles can be an effective way to evaluate the impact of sulfate aerosols on regional haze formation.     

Effects of tetrakis (hydroxymethyl) phosphonium sulfate pretreatment on characteristics of sewage sludge

Recently, tetrakis(hydroxymethyl)phosphonium sulfate(THPS) was found to play an important role in the sludge pretreatment process. However, the effects of THPS pretreatment on the characteristics of sewage sludge are still insufficiently understood.The properties of sludge after pretreatment with different concentrations of THPS were investigated in this study. The results showed that pH, dewatering ability, and particle size of sludge decreased with increase in THPS concentration. The volatile suspended solids(VSS) and total suspended solids(TSS) of sludge also decreased slightly with increase in THPS concentration. The specific oxygen uptake rate(SOUR) results suggested that lower THPS concentrations(≤ 1.87 mg/g VSS) enhanced the activity of sludge, but higher concentrations(≥ 1.87 mg/g VSS) inhibited it. Gram-negative bacteria with peritrichous flagellation(such as Pseudomonas, Escherichia, and Faecalibacterium) were extremely sensitive to THPS. The decrease in specific most probable numbers(MPNs) of pathogens(total coliforms and Escherichia coli) with the increase in THPS concentration also proved the sterilization ability of THPS in the sludge pretreatment process. Pretreatment of sludge with concentrations of THPS higher than 37.41 mg/g VSS would meet the pathogen requirements for land application of Class A biosolids.     

ANAMMOX培养物中硫酸盐型氨氧化生物转化机制

厌氧条件下,ANAMMOX培养物中发生的硫酸盐型氨氧化（SRAO）现象被认为是由ANAMMOX细菌（AnAOB）介导的自养生物转化过程.在这个过程中,作为电子供体的氨被电子受体硫酸盐氧化.在某一些自然环境中观察到的氨与硫酸盐转化现象也被认为是由于上述生物转化作用而导致的.然而,在不同研究中,关于氨与硫酸盐的转化摩尔比（N/S）、硫酸盐还原的中间产物和最终产物的认定均有存在较大差异.因此,氨和硫酸盐在ANAMMOX培养物中的转化机制仍不明确.为探明ANAMMOX污泥中SRAO现象背后的基质转化途径,在不同厌氧状态（微氧：-100 mV < ORP < 0 mV,0.5 mg·L^-1 < DO < 1 mg·L^-1;缺氧：-300 mV < ORP < -100 mV,0.2 mg·L^-1 < DO < 0.5 mg·L^-1;厌氧：ORP < -300 mV,DO < 0.2 mg·L^-1）以及不同污泥组成（ANAMMOX污泥和混合污泥）的条件下开展连续流实验和批次实验.结果表明,SRAO现象只能在缺氧条件且存在异养硫酸盐还原细菌（SRB）的混合污泥中发生;在ANAMMOX污泥中无论处于哪种厌氧状态,均不会发生SRAO现象.微生物群落变化与功能基因表达分析表明,ANAMMOX污泥和混合污泥中均存在以Nitrosomonas和Nitrosospira为主的携带amoA基因的氨氧化细菌（AOB）,可将氨氧化生成亚硝酸盐,为AnAOB代谢提供底物.Desulfomicrobium、Desulfovibrio以及Desulfonatronum等携带apsA基因的SRB只存在于混合污泥中,它们利用微生物衰亡释放的有机物将硫酸盐还原.AnAOB并不能以硫酸盐为电子受体氧化氨维持代谢.因此,在ANAMMOX污泥中观察到的SRAO现象（即氨与硫酸盐的同步转化）实际上是氨氧化、ANAMMOX和异养硫酸盐还原这3个过程联合的结果,上述生物转化过程分别由AOB、AnAOB和SRB完成.     

酸浸渣制取硫酸亚铁的研究

论述了利用金矿冶炼中的酸浸尾渣制取硫酸亚铁溶液，主要考察了温度、反应时间、硫酸浓度、硫酸用量对铁浸出率的影响，得出了酸浸尾渣制取硫酸亚铁的最佳工艺条件。     

Polytitanium sulfate (PTS): Coagulation application and Ti species detection

Interest in the development of inorganic polymerized coagulants is growing; however, there are only limited studies on the synthesis of polytitanium coagulants, which are expected to exhibit improved coagulation efficiency with better floc properties. This study presents the synthesis of polytitanium sulfate (PTS) for potential application in water purification, followed by characterization of PTS flocs and titanium species detection. Stable PTS solutions were successfully synthesized and standard jar tests were conducted to evaluate their coagulation efficiency. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) speciation analysis revealed that a variety of mononuclear and polynuclear complexes were formed in PTS solution, indicating the polymeric nature of the synthesized coagulant. Floc characteristics were studied through on-line monitoring of floc size using a laser diffraction particle size analyzer. Results showed that PTS had a comparable or in some cases even higher organic matter and particulate removal efficiency than Ti(SO₄)₂. The effluent pH after PTS coagulation significantly improved toward desirable values closer to neutral pH. Properties of flocs formed by PTS were significantly improved in terms of floc size, growth rate and structure. This study showed that PTS could be an efficient and promising coagulant for water purification, with the additional benefit that its coagulated sludge can be used to recover valuable TiO₂ nanoparticles for various commercial applications.     

硫酸渣制备高纯度硫酸亚铁

以高铁硫酸渣为原料,采用酸浸-还原-除杂-结晶一重结晶-干燥工艺,合成高纯度硫酸亚铁。通过反应温度、反应时间对硫酸渣中铁的浸出率的影响,以及结晶温度、干燥温度、干燥时间对硫酸亚铁产品纯度的影响做分析实验,得出最佳酸浸条件：硫酸渣与硫酸的固液比为1：3,硫酸质量分数为20％～25％,反应温度为80℃,反应时间为6h,搅拌强度为200r／min;最佳结晶精制条件：结晶溶液pH值为1-3,温度为60℃;除杂最佳条件：pH值约为4．5;冷却结晶温度控制在20℃,结晶干燥过程为30℃,干燥6h。