Chemical characteristics of acidified waters in southwest China

ＣｈｅｍｉｃａｌｃｈａｒａｃｔｅｒｉｓｔｉｃｓｏｆａｃｉｄｉｆｉｅｄｗａｔｅｒｓｉｎｓｏｕｔｈｗｅｓｔＣｈｉｎａＬｅｉＺｈｉｈｏｎｇ；ＬｉａｎｇＸｉａｏｍｉｎｇ；ＸｕＸｉａｏｑｉｎｇ；ＸｉａＹｉｃｈｅｎｇ（ＩｎｓｔｉｔｕｔｅｏｆＨｙｄｒｏｂｉｏｌｏｇ...     

水稻土对磷的吸持能力及环境风险研究

以湖南Cd污染区水稻土为供试土壤,研究了土壤活性Al(Al_(ox))、活性Fe(Fe_(ox))、磷吸持指数(PSI)、吸持饱和度(DPSS)和释放风险指数(ERI)及其相关性关系.结果表明:供试水稻土中Al_(ox)和Fe_(ox)含量变异性较大,分别为55.67~1495.90 mg·kg~(-1)和1.50~13.63 g·kg~(-1),但有效磷含量变化幅度不大.水稻土吸持磷能力较弱,全部样品中PSI均低于30,但水稻土磷的吸持饱和度较低,85%的土壤样品DPSS低于磷淋失临界值(15%),且磷释放失风险(ERI)较小.水稻土中Al_(ox)含量和Fe_(ox)含量与PSI存在显著正相关关系(p0.05),而与DPSS之间表现为显著负相关关系(p0.01),DPSS和PSI呈现为显著负相关关系(p0.01).     

铁活化过二硫酸盐湿法氧化去除一甲胺恶臭气体

CH₃NH₂(一甲胺)作为一种重要的工业原料而被大量使用,其嗅阈值低,具有刺鼻的鱼臭味,是一种典型的恶臭气体. 选取PS(过二硫酸盐)作为氧化剂,采用湿法吸收氧化去除CH₃NH₂. 在探讨CH₃NH₂的吸收性能的基础上,比较了4种方式〔Fe2+活化PS、CA(柠檬酸)螯合Fe2+活化PS、Fe0活化PS、CA联合Fe0活化PS〕对CH₃NH₂湿法氧化去除效果的影响. 结果表明:CH₃NH₂ 气体在酸性条件下易溶于水;单独用Fe2+或Fe0活化PS处理CH₃NH₂时,Fe0活化后的去除效果明显优于Fe2+;然而,在联合使用螯合剂CA之后,Fe2+活化的去除效果反而优于Fe0. CA螯合Fe2+的CH₃NH₂去除率由单独Fe2+活化时的32%升至64%,Fe0活化与CA联合Fe0活化去除率均提升至40%. 究其原因,可能是由于不同活化方式下Fe2+释放速率不同所致,释放速率直接影响了Fe2+的存在时间,Fe2+活化PS速率对于氧化去除效果有影响,并最终影响CH₃NH₂的脱除.      

Inhibition and dispersion of polyepoxysuccinate as a scale inhibitor

The inhibition and dispersion of polyepoxysuccinate (PESA, self-manufactured) to inorganic scale was evaluated by scale static beaker test to CaC0₃ and Ca₃(P0₄)2, stability test to zinc salt, and dispersion test to ferric oxide. The experimental results demonstrated that PESA functioned excellent scale inhibition to CaC0₃ and Ca₃(P0₄)₂, good stability to zinc salt and special dispersion to ferric oxide. Under the water with hardness 500-1200 mg/L, alkalinity 1000 mg/L, and dosage of PESA 31.2 mg/L, PESA scale inhibition ratio reached more than 85.0%. At dosage of PESA 20.8 mg/L inhibition ratio on calcium phosphate reached 38.9%, at optimum dosage of PESA 9.1 mg/L, the stability ratio was up to 96.1%; while at dosage of PESA 3.6 mg/L, transmittance ratio reached 64.4%. Therefore, PESA can be considered a soluble, high effective and versatile inhibitor.     

聚合氯化铝中纳米Al13电荷特性及其混凝效果

采用聚丙烯酰胺凝胶柱层析法分离纯化聚合氯化铝(PAC)中的Al₁₃形态,并采用Al-Ferron逐时络合比色法和ZATESIZER 3000HSA测定仪对分离所得纳米Al₁₃形态以及AlCl₃和PAC进行了分析表征和电荷特性的对比性研究;采用烧杯实验法对3个样品处理实际和模拟水样的混凝效果进行了对比性研究.Al-Ferron逐时络合比色法的结果表明,采用层析法分离可得到含量99%左右的纳米Al₁₃形态;电荷特性和混凝效果研究结果表明纳米Al₁₃形态较其它两者具有更好的除浊、除腐殖酸和脱色效果并且具有更强的电中和能力,因此Al₁₃形态是一种具有较高正电荷和较高的水解稳定性,在给水和废水处理中的一种较为有效的Al形态.     

Behavior of the herbicide dimepiperate with homoionic clays in aqueous solution

Ｂｅｈａｖｉｏｒｏｆｔｈｅｈｅｒｂｉｃｉｄｅｄｉｍｅｐｉｐｅｒａｔｅｗｉｔｈｈｏｍｏｉｏｎｉｃｃｌａｙｓｉｎａｑｕｅｏｕｓｓｏｌｕｔｉｏｎ￥ＬｉｕＷｅｉｐｉｎｇ；ＷａｎｇＱｉｑｕａｎ；ＳｈａｏＹｉｎｇ；ＪｉＪｉｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉ...     

残留药剂对土壤As、Hg、Cd、Pb浸出测试干扰及消除方法

固化/稳定化是应用最广泛的重金属污染土壤修复技术,但残留药剂在浸出测试过程对土壤二次修复导致的验收假达标风险未引起充分重视.本研究分别采用Fe₂（SO₄）₃、Na₂S和KH₂PO₄修复As、Hg、Cd-Pb污染土壤,探究不同养护反应时间、药剂混合均匀度和投加量等工艺条件下土壤重金属浸出浓度差异,验证液相二次修复干扰效应的发生,并考察Cu²⁺和Al³⁺等竞争剂对土壤残留KH₂PO₄药剂干扰的消除效果,提出最佳的残留药剂消除方法.结果表明,分别投加6.7%的Fe₂（SO₄）₃、6.7%的Na₂S和3.3%的KH₂PO₄修复含As、Cd和Pb土壤时,土壤中各重金属浸出浓度从第0 d起分别持续小于0.05、0.5和1.6 mg·L^-1,稳定化效率分别保持在99%、83%~99%和97%~98%.投加0.0008%的Na₂S修复土壤Hg时,Hg浸出浓度自第0 d起随养护反应时间显著下降,稳定化效率维持在78%~88%.虽然修复后土壤中Hg浸出浓度随药剂混合均匀度增加而显著下降,As、Cd、Pb浸出浓度在混合均匀度为67%和33%时相较混合均匀度为100%时均无显著变化（1.7% Fe₂（SO₄）₃修复组除外）,但均小于无二次反应理论值.此外,Cu²⁺能与Pb²⁺竞争浸出液中的残留PO₄^3-减弱干扰效应,当Cu²⁺优化投加量为5.7%、11.3%、14.2%时,混合均匀度67%处理组Pb浸出浓度分别升至理论值的51%、72%、84%,混合均匀度33%处理组Pb浸出浓度则分别升至理论值的38%、71%、81%.而Al³⁺无法与Pb²⁺竞争PO₄^3-,甚至对土壤Pb具有显著活化效果.Cu²⁺对Pb也具有一定的活化效果,因此,需控制Cu²⁺投加量以寻求活化效果与优化作用的最佳平衡点.     

Adsorption of herbicide triclopyr on homoionic clays

ＡｄｓｏｒｐｔｉｏｎｏｆｈｅｒｂｉｃｉｄｅｔｒｉｃｌｏｐｙｒｏｎｈｏｍｏｉｏｎｉｃｃｌａｙｓＬｉｕＷｅｉｐｉｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＺｈｅｊｉａｎｇＵｎｉｖｅｒｓｉｔｙ，Ｈａｎｇｚｈｏｕ３１００２７，Ｃｈｉｎａ）ＡｌｂａＰｕ...     

Electrolyte effects on aqueous atmospheric oxidation of sulphur dioxide by hydrogen peroxide

The rate of oxidation of sulphur dioxide by hydrogen peroxide in the presence of various supporting electrolytes has been determined by the stopped flow method. In a sodium perchlorate medium (chosen as reference electrolyte) first-order kinetics were observed with respect to HSO₃⁻, H₂O₂ and H⁺. The influence of the ionic strength was investigated and the third-order rate constant was calculated at infinite dilution. The rate constants of the reaction are shown to be far higher when chloride or ammonium ions are added to the solution.The effect of temperature and traces of metals ions (Mn²⁺, Fe²⁺, Fe³, Cu²⁺, Cr³⁺) was studied. The oxidation reaction is virtually insensitive to the effects of Mn²⁺, Fe³⁺, Cu²⁺ and Cr³⁺. Catalytic activity is observed with Fe²⁺.     

不同氧化还原环境对煤矸石污染物质释放的影响

为评价不同氧化还原环境对煤矸石污染物质释放的影响,设置处理1(充氧饱和的曝气去离子水,Eh=229mV)、处理2(煮沸30min的去离子水,Eh=250mV)两种氧化环境及处理3(添加富含有机质的过滤养殖废水,Eh=14mV)一种还原环境的水溶液做浸提剂,对煤矸石进行0～9d的连续振荡浸提试验.结果表明:在浸提初期(0～1d内),煤矸石表面已形成的氧化产物迅速溶出,使得两种氧化环境和还原环境下的煤矸石浸出液pH都迅速降低,EC、Eh及多种溶出离子浓度迅速升高,但还原环境下煤矸石浸出液中Cu、F-浓度变化不显著,且还原环境下浸出液中其他离子虽有上升但显著低于氧化环境下.随浸提时间延长(1～9d),两种氧化环境下煤矸石浸出液pH继续降低,浸出液中Fe、Mn、Cu、Zn和SO2-4、F-多种污染物质溶出数量明显增加并呈现典型的持续氧化产酸过程;而还原环境下煤矸石浸出液的pH随时间延长降低不明显,Fe、Mn、Zn等污染物质溶出数量显著低于两种氧化环境下,Cu和SO2-4的释放也受到明显抑制.说明还原环境能有效抑制煤矸石氧化产酸及多种污染物质的溶出,且显著低于氧化环境.因此,在煤矸石堆场投加有机质形成还原(厌氧)环境可进行矸石污染的原位控制及治理.     

Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts

Decomposition of hexachlorobenzene (HCB) was investigated over several metal oxides (i.e., MgO, CaO, BaO, La₂O₃, CeO₂, MnO₂, Fe₂O₃, and Co₃O₄) supported on Al₂O₃, which was achieved in closed system at a temperature of 300°C. Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents. The decomposition efficiency of different catalysts for this reaction depends on the nature of the metal oxide used, and Al₂O₃ supported La₂O₃ was found to be the most active one. Pentachlorobenzene (PeCB), and all tetrachlorobenzene (TeCB), trichlorobenzene (TrCB), and dichlorobenzene (DCB) isomers were detected after the decomposition reaction, indicating that the decomposition was mainly a dechlorination process. The detection of all lower chlorinated benzenes suggested the complexity of decomposition and the presence of more than one dechlorination pathway.     

亚热带可变电荷土壤磷素淋失临界点及其与土壤特性的关系

选取我国亚热带地区16种典型可变电荷土壤,通过室内模拟试验测定其磷素(P)淋失临界点的Olsen-P含量,以及可能对其构成有影响的8个化学性质指标(pH、CEC、粘粒、有机质、交换性钙、镁和铁铝氧化物含量),以探讨可变电荷土壤P淋失临界点的特点及其与土壤相关性质的关系,并评价当前的P淋失潜在风险.结果表明:可变电荷土壤P淋失临界点的Olsen-P含量(56 ～ 123 mg·kg-1)差异很大,旱地土壤临界点Olsen-P含量主要集中在低值区间(＜60 mg·kg-1),而水稻土临界点Olsen-P含量集中在高值区间(＞80 mg·kg-1);旱地土壤P淋失风险高于水稻土.主成分分析显示,可变电荷土壤的pH、粘粒、CEC、有机质、交换性钙镁、氧化铁铝等化学性质同时对其临界点Olsen-P含量构成正的或负的影响.因此,临界点Olsen-P含量与单一因素的回归分析不仅不能够确切地反映临界点Olsen-P含量与这些化学性质的关系(与pH、CEC、粘粒、交换性钙镁含量无显著相关),甚至与理论上的关联相违(与氧化铁铝含量呈负相关).与以往研究结果比较,可变电荷土壤在旱作和稻作下的P淋失临界点的Olsen-P含量都普遍高于永久电荷土壤,研究的16种可变电荷土壤的实际Olsen-P含量也远低于临界点Olsen-P含量,由此推断南方地区耕作土壤的P淋失风险仍较小.     

异步周期换向电凝聚法处理活性艳蓝X-BR模拟染料废水及其机理研究

针对传统电凝聚法处理废水过程中易出现的电极表面钝化和极化而影响处理效果的现象,采用铝和铁板作为两极同步换向方法,通过周期性改变电流方向使电极钝化和极化现象得以减缓或消失,并实现两极均可溶,利用铝、铁系无机絮凝剂共存时可提高处理效果的特点,对活性艳蓝X-BR模拟染料废水进行处理;通过正交试验,获得了该方法的最佳处理条件.在此基础上,为避免金属铝成分在废水中出现剩余影响水质,采用异步周期换向方式加以改进,考察了铝、铁电极不同通电时间对处理效果的影响,并利用紫外-可见光分光光度法、高效液相色谱法、ICP法、高分辨质谱技术、激光粒度分析仪等手段对废水处理过程主导因素和污染物去除机理以及该方法对强化处理效果的作用机理进行了分析.研究表明,最佳条件下采用异步换向周期电凝聚法处理活性艳蓝X-BR模拟染料废水30 min可使模拟废水脱色率接近100%,COD去除率可达76%以上;处理过程中起主导作用的是电凝聚过程而非电氧化还原过程;除大部分染料分子被电凝聚气浮或沉降导致脱色外,其余的活性艳蓝X-BR染料分子在电解作用下首先断裂生成了1,4-二氨基蒽醌-2-磺酸根,之后1,4-二氨基蒽醌-2-磺酸根又被直接絮凝上浮或沉降,或者在氢离子作用下发生了加氢反应使双键消失而脱色,模拟废水脱色是上述作用的综合结果.采用改进后的异步周期换向电凝聚法可以使铝铁离子凝聚过程形成的絮体具有更为合理的粒度和结构特性,从而更易于被去除,因此处理效果略优于同步换向和定向电流电凝聚过程,且可以实现处理后废水中铝离子含量降低到无法检出,避免其在处理后的废水中出现剩余影响水质.     

Species distribution of polymeric aluminium-ferrum--timed complexation colorimetric analysis method of Al-Fe-Ferron

ＩｎｔｒｏｄｕｃｔｉｏｎＴｕｒｎｅｒｆｉｒｓｔａｄｏｐｔｅｄｔｈｅＡｌ ｆｅｒｒｏｎｍｅｔｈｏｄａｓａｎｉｎｄｉｒｅｃｔａｎａｌｙｓｉｓｍｅｔｈｏｄｔｏｄｅｔｅｒｍｉｎｅｔｈｅｓｐｅｃｉｅｓｄｉｓｔｒｉｂｕｔｉｏｎｏｆＡｌ ｓｏｌｕｔｉｏｎｓｉｎ 1969(Ｔｕｒｎｅｒ,1969) .Ｔｈｉｓｍｅｔｈｏｄｈａｓｂｅｅｎｉｍｐｒｏｖｅｄａｎｄｉｓｓｔｉｌｌｕｓｅｄａｔｐｒｅｓｅｎｔａｎｄｉｔｐｌａｙｓａｋｅｙｒｏｌｅｉｎｓｔｕｄｙｉｎｇｔｈｅｄｉｓｔｒｉｂｕｔｉｏｎａｎｄｔｒａｎｓｆｏｒｍａｔｉｏｎｏｆｓｐｅｃｉ…     

Metal ion catalyzed oxidation of SO2 in the presence of trace H2O2 in aqueous solution under environmental reaction conditions

Aqueous phase oxidation of SO₂ or S(IV) by H₂O₂-metal ions at a H₂O₂ concentration much lower than S(IV), was studied using a continuously flowing stirred reactor. Of the metal ions, Fe²⁺ showed the highest catalytic activity, i.e. the oxidation of S(IV) continued after most of the H₂O₂ was consumed. The dependence of the rate on the concentration of S(IV), H₂O₂, Fe²⁺ or H⁺ and temperature was determined. The following rate expression and low apparent activation energy of 40.7 kJ mole⁻¹ were evaluated,−d[S(IV)]/dt=620[S(IV)]²[Fe²⁺]^0.5(molel⁻¹S⁻¹). The significance of this reaction as the sulfate formation in atmospheric water droplets is discussed and a comparison of the rate with others using H₂O₂, O₃ and dissolved O₂ catalyzed by metal ions is made.     

冶金尘泥混合垃圾燃烧飞灰熔融重构固化重金属的研究

针对冶金固废组分复杂且难以高附加值利用的特性,结合当前垃圾燃烧飞灰重金属污染现状,通过将两者混合进行熔融固化及成分重组,研究了重金属固化及浸出毒性.结果表明:随着温度升高,固化渣出现明显结块,且燃烧过程中矿物发生重组,Zn、Cu、Pb和Cr取代硅酸盐中Ca~(2+)、Al~(3+)等离子而被固熔于网状基体中,生成了Cu_6Zn_4Al_2O_4、FeCr_2O_4、Cd_(0.75)Zn_(0.25)Fe_2O_4、Zn(AlO0.5Fe1.5)O4、MgCr0.4Fe1.6O4及Cu0.5Zn0.5Fe2O4等物质;且随着温度升高,Ca-Fe-Si-O体系形成一种耐热硅酸盐稳定相CaFe_3(SiO_4)2OH,由于其覆盖或包裹住含有重金属的晶体,从而延缓并阻止了灰渣分解及重金属的浸出,降低了重金属对环境的污染.     

支化聚乙烯亚胺功能化磁性纳米吸附剂的制备及对Cu2+的吸附研究

为解决水体中重金属Cu²⁺污染,本研究首先采用水热法制备得到超顺磁四氧化三铁纳米粒子,然后使用对Cu²⁺具有强络合作用的含有丰富氨基官能团的支化聚乙烯亚胺接枝到纳米粒子表面,得到Fe₃O₄@BPEI磁性纳米吸附剂。采用红外光谱(FTIR)、X射线粉末衍射(XRD)、透射电子显微镜(TEM)等对其结构、尺寸及形貌进行表征。研究了不同吸附因素对吸附剂吸附Cu²⁺的影响,确定了最佳吸附条件,并通过吸附动力学模型和吸附等温线模型进一步探讨吸附机理。结果表明：支化聚乙烯亚胺成功接枝到四氧化三铁纳米粒子表面。最佳吸附条件为pH=6.0、吸附平衡时间为40 min、吸附剂用量为10 mg。通过实验数据拟合,Fe₃O₄@PEI吸附Cu²⁺的过程符合Langmuir等温吸附方程和拟二级动力学模型,表明吸附过程为化学吸附控制的单分子层覆盖,在303 K时,模型理论饱和吸附量为141.24 mg/g。表明支化聚乙烯亚胺修饰的磁性纳米吸...     

Oxidative removal of acetaminophen using zero valent aluminum-acid system: Efficacy, influencing factors, and reaction mechanism

Commercial available zero valent aluminum under air-equilibrated acidic conditions (ZVAl/H⁺/air system) demonstrated an excellent capacity to remove aqueous organic compounds. Acetaminophen (ACTM), the active ingredient of the over-the-counter drug Tylenol^®, is widely present in the aquatic environment and therefore the treatment of ACTM-contaminated water calls for further research. Herein we investigated the oxidative removal of ACTM by ZVAl/H⁺/air system and the reaction mechanism. In acidic solutions (pH < 3.5), ZVAl displayed an excellent capacity to remove ACTM. More than 99% of ACTM was eliminated within 16 hr in pH 1.5 reaction solutions initially containing 2.0 g/L aluminum and 2.0 mg/L ACTM at 25 ± 1\textcelsius. Higher temperature and lower pH facilitated ACTM removal. The addition of different iron species Fe⁰, Fe²⁺ and Fe³⁺ into ZVAl/H⁺/air system dramatically accelerated the reaction likely due to the enhancing transformation of H₂O₂ to HO. via Fenton's reaction. Furthermore, the primary intermediate hydroquinone and the anions formate, acetate and nitrate, were identified and a possible reaction scheme was proposed. This work suggested that ZVAl/H⁺/air system may be potentially employed to treat ACTM-contaminated water.     

Hydrogeochemical and mineralogical characteristics related to heavy metal attenuation in a stream polluted by acid mine drainage: A case study in Dabaoshan Mine, China

Dabaoshan Mine, the largest mine in south China, has been developed since the 1970s. Acid mine drainage (AMD) discharged from the mine has caused severe environmental pollution and human health problems. In this article, chemical characteristics, mineralogy of ocher precipitations and heavy metal attenuation in the AMD are discussed based on physicochemical analysis, mineral analysis, sequential extraction experiments and hydrogeochemistry. The AMD chemical characteristics were determined from the initial water composition, water-rock interactions and dissolved sulfide minerals in the mine tailings. The waters, affected and unaffected by AMD, were Ca-SO₄ and Ca-HCO₃ types, respectively. The affected water had a low pH, high SO₄^2- and high heavy metal content and oxidation as determined by the Fe²⁺/Fe³⁺ couple. Heavy metal and SO₄^2- contents of Hengshi River water decreased, while pH increased, downstream. Schwertmannite was the major mineral at the waste dump, while goethite and quartz were dominant at the tailings dam and streambed. Schwertmannite was transformed into goethite at the tailings dam and streambed. The sulfate ions of the secondary minerals changed from bidentate- to monodentate-complexes downstream. Fe-Mn oxide phases of Zn, Cd and Pb in sediments increased downstream. However, organic matter complexes of Cu in sediments increased further away from the tailings. Fe³⁺ mineral precipitates and transformations controlled the AMD water chemistry.