地下水修复系统中释氧材料的改进及pH调控

在采用释氧材料的地下水污染修复系统中,释氧材料提供溶解氧的同时,往往造成体系pH的升高。针对这一问题,将过氧化钙(CaO2)、水泥、河沙、膨润土和KH2PO4按一定比例混合在一起制作了3种释氧材料,并在柱实验中观测了不同释氧材料对水体溶解氧(DO)及pH值的影响。实验数据表明,水泥对释氧材料的缓释作用明显,有助于保证释氧速率平稳,避免由于释氧材料反应过快所带来的高pH问题;在释氧材料中添加一定量KH2PO4(质量分数小于10%),可以起到缓冲体系pH值的作用,并且不会造成修复系统磷污染;电气石具有降低溶液高pH值的作用,以粒径为1～2 mm的电气石作缓冲介质可以将体系pH值由11.3降至10.2。     

新型释氧材料制备及对湿地堵塞解除研究

针对人工湿地内部DO含量较低引起的生物性堵塞,污水处理效率下降的问题,采用投加释氧材料的方法来提高湿地内部DO含量,修复生物性堵塞。采用CaO_2为释氧剂制备释氧材料,进行释氧性能研究。结果表明:采用大孔弱酸性丙烯酸系阳离子交换树脂作为包埋剂制成的释氧材料释氧性能最佳。在模拟人工湿地污水系统中,释氧材料可使反应器中DO质量浓度在15d内保持在5.0mg/L以上,并且pH保持中性水平,相较未投加释氧材料的对照组,30d内COD的平均降解效率提高125%。投加释氧材料可以使发生生物性堵塞的人工湿地系统在连续运行条件下基质孔隙率在15d内恢复到初始水平的83%左右,并且相较机械曝气具有操作便捷、不受环境限制以及成本低廉的优点。     

CPC/CaO2氧缓释复合材料的制备及其释氧性能探讨

利用过氧化钙（CaO2）遇水释放氧气的特性,采用混合法将CaO2载入到磷酸钙骨水泥（CPC）中,并通过挤出-滚圆造粒方法制备出CPC/CaO2氧缓释复合材料,旨在为污染地下水的好氧生物修复技术提供一种长期、高效的供氧源。由X射线衍射（XRD）分析可知,通过固相反应制取的CPC主要成分为Ca5（PO4）3（OH）和Ca10（PO4）6（OH）2,具有较快的固化时间和固化效果;CPC/CaO2氧缓释复合材料分3个阶段进行释氧,其中2、3阶段分别符合一级和零级释氧动力学特征,且其释氧速率和释氧周期得到明显改善。本研究成果可用于实际地下水修复工程,解决污染地下水原位生物修复过程中溶解氧（DO）的输送问题。     

CPC/CaO_2氧缓释复合材料的制备及其释氧性能探讨

利用过氧化钙(CaO2)遇水释放氧气的特性,采用混合法将CaO2载入到磷酸钙骨水泥(CPC)中,并通过挤出-滚圆造粒方法制备出CPC/CaO2氧缓释复合材料,旨在为污染地下水的好氧生物修复技术提供一种长期、高效的供氧源。由X射线衍射(XRD)分析可知,通过固相反应制取的CPC主要成分为Ca5(PO4)3(OH)和Ca10(PO4)6(OH)2,具有较快的固化时间和固化效果;CPC/CaO2氧缓释复合材料分3个阶段进行释氧,其中2、3阶段分别符合一级和零级释氧动力学特征,且其释氧速率和释氧周期得到明显改善。本研究成果可用于实际地下水修复工程,解决污染地下水原位生物修复过程中溶解氧(DO)的输送问题。     

紫外辐照改性生物炭对土壤中Cd的稳定化效果

以废椰子壳为原料制备生物炭,采用365 nm紫外光辐照改性生物炭,探究改性生物炭对土壤中Cd的钝化效果。通过改性生物炭对溶液中Cd~(2+)的等温吸附实验表明,经过16 h辐照后的生物炭吸附效果最好,对溶液中Cd~(2+)的吸附量可达67.46 mg·kg~(-1)。通过添加不同生物炭含量(0、1%、3%、5%和10%)对土壤中Cd的修复实验发现,生物炭的添加可以提高酸性土壤的pH值,但经紫外辐照改性后的生物炭对pH值改变能力不如未改性生物炭。此外,生物炭的添加可使土壤中弱酸提取态和可还原态Cd向可氧化态转化,紫外辐照改性可显著提高这一能力。改性生物炭对土壤中Cd的钝化与表面含氧官能团有关。     

复合介质渗透反应格栅去除地下水中的氨氮

针对受低浓度氨氮污染的地下水,实验筛选组合了不同的反应介质,利用串联的多介质填充柱模拟渗透反应格栅,通过物理吸附及生物硝化-反硝化作用来实现氮的去除。结果表明,在进水氨氮浓度为10 mg/L、流速为0.5 m/d的条件下,模拟柱对氨氮的去除率达到98%以上,且不会出现亚硝酸盐及硝酸盐浓度的升高。水体经过释氧柱后溶解氧由2mg/L升高至10 mg/L以上,表明释氧材料可提供硝化细菌所需的好氧环境。好氧柱中填充易于生物挂膜的生物陶粒及对氨氮有较强吸附能力的沸石,二者联用通过生物硝化-物理吸附协同作用实现对氨氮的去除,其中生物作用实现的氨氮去除量占总去除量的50%左右。后续厌氧反应柱填充海绵铁除氧并利用松树皮颗粒作为碳源,创造反硝化菌生长条件,硝酸盐氮浓度可由10 mg/L降低至5 mg/L以下,实现对好氧反应阶段所产生的硝酸盐的去除,避免了地下水的二次污染。     

催化铁与生物法耦合除磷工艺特性

为了研究催化铁与生物耦合后对生物除磷特性的影响，实验采用人工配水用厌氧／好氧间歇流式富集培养聚磷微生物。对比发现，催化铁与生物耦合组中厌氧末段ORP降低了约60mV，pH值小幅度的上升（≤0．3），整个培养过程中铁离子的浓度开始快速增加，之后趋于稳定（约40mgFe／gMLSS）。对好氧末段污泥SVI值比较发现，耦合工艺污泥沉降性能得到改善。除磷曲线比较发现，耦合组中厌氧末段磷的释放量下降，而好氧阶段磷的吸收速率增加；胞内聚合物提取表明，耦合组厌氧末段聚磷菌细胞内PHA含量有提高，好氧末段糖原含量有下降。磷形态提取分析表明，耦合组好氧末段污泥中无机态PO3 4-- P含量更高。低浓度铁离子可以起到与生物耦合同步除磷的目的，本工艺长期运行未发现耦合体系中催化铁对除磷的抑制作用。     

生物炭复配磷酸盐对Pb-Cd污染土壤原位钝化修复的研究

采用小区试验方法,选取生物炭、磷酸盐及两者复配材料作为钝化剂原位修复工业遗留场地Pb-Cd污染土壤,通过毒性浸出方法(TCLP)以及欧共体标准物质局(BCR)连续提取法分析钝化修复效果,以期获取最优化的钝化修复方法。结果表明,生物炭、磷酸盐及两者复配材料均能够有效降低土壤Pb、Cd的生物有效性和迁移能力。生物炭能提高土壤pH,使TCLP提取态Pb、Cd分别降低56.26%和83.54%,生物炭能促进重金属沉淀的形成进而提升残渣态Pb、Cd比例;磷酸盐主要通过矿物沉淀作用促使重金属由弱结合态向强结合态方向的转化,使TCLP提取态Pb、Cd分别降低70.66%、89.94%,残渣态Pb、Cd比例显著提升,进而有效降低Pb、Cd的生物有效性和迁移能力。生物炭和磷酸盐复配材料相比单一钝化剂材料未表现出协同作用,但复配材料在保证钝化修复效果的前提下,能补偿酸性磷酸盐造成的土壤酸化,在修复实践中更具应用优势。     

催化铁与生物法耦合除磷工艺特性简

为了研究催化铁与生物耦合后对生物除磷特性的影响，实验采用人工配水用厌氧/好氧间歇流式富集培养聚磷微生物。对比发现，催化铁与生物耦合组中厌氧末段ORP降低了约60 mV，pH值小幅度的上升（≤0.3），整个培养过程中铁离子的浓度开始快速增加，之后趋于稳定（约40 mg Fe/g MLSS）。对好氧末段污泥SVI值比较发现，耦合工艺污泥沉降性能得到改善。除磷曲线比较发现，耦合组中厌氧末段磷的释放量下降，而好氧阶段磷的吸收速率增加；胞内聚合物提取表明，耦合组厌氧末段聚磷菌细胞内PHA含量有提高，好氧末段糖原含量有下降。磷形态提取分析表明，耦合组好氧末段污泥中无机态PO^3-₄-P含量更高。低浓度铁离子可以起到与生物耦合同步除磷的目的，本工艺长期运行未发现耦合体系中催化铁对除磷的抑制作用。     

阳极pH对Fe(Ⅲ)强化阴极电动修复Pb污染土壤的影响

土壤的pH值对电动力修复技术至关重要。利用Fe(NO3)3作为阴极电解液,不仅可以消耗电解产生的OH-,不会对土壤造成二次污染,并且修复后土壤的pH相对较低。在土壤室和阴极室之间添加活性炭纤维和阳离子膜,增强修复效果。采用配制的Pb污染土壤,在电场强度为1 V·cm-1的条件下进行实验,研究不同pH(3、4、5)的柠檬酸-柠檬酸钠阳极电解液对电动力学修复Pb污染土壤效果的影响。结果表明:在利用Fe(Ⅲ)-活性炭纤维强化电动修复时,添加的阳极电解液pH值越小,Pb的去除效果越好;各阳极电解液pH值递增梯度相对应Pb的截面最大去除率分别为:80.53%、53.1%和40.69%。通过分析残留在土壤中Pb的重金属形态,得到在距离阳极4 cm处的土壤截面中Pb主要以较稳定的、环境毒性较低的有机态和残渣态存在。     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

Acidification of a solonetzic soil by nitrogenous fertilizers

Abstract

Annual applications of (NH₄)₂SO₄ NH₄NO₃ and urea on a Solonetzic soil at 112 kg N/ha for 10 consecutive years reduced pH levels from 5.6 for the check to 4.4, 4.9 and 5.3, respectively for (NH₄)₂SO₄, NH₄NO₃ and urea. (NH₄)₂SO₄ generated twice as much exchange acidity as NH₄NO₃ and four times as much as urea. Net extractable cations leached from the Ap horizon closely approximated the amount of exchange acidity generated by (NH₄)₂SO₄ and NH₄NO₃ fertilizers. The levels of soil extractable Al and Mn were greatly enhanced by (NH₄)₂SO₄ as were plant contents. Similar acidifying effects to that produced by the (NH₄)₂SO₄ occurred when NH₄NO₃ was applied at 300 kg N/ha annually for 12 consecutive years in another field experiment on the same soil. Liming samples of the field (NH₄)₂SO₄ acidified soils in the greenhouse, significantly increased yields and lowered the Al and Mn contents of the plants to normal levels.     

Bioremediation of a diesel fuel contaminated aquifer: simulation studies in laboratory aquifer columns

The in situ bioremediation of aquifers contaminated with petroleum hydrocarbons is commonly based on the infiltration of groundwater supplemented with oxidants (e.g., O₂, NO₃⁻) and nutrients (e.g., NH₄⁺, PO₄³⁻). These additions stimulate the microbial activity in the aquifer and several field studies describing the resulting processes have been published. However, due to the heterogeneity of the subsurface and due to the limited number of observation wells usually available, these field data do not offer a sufficient spatial and temporal resolution. In this study, flow-through columns of 47-cm length equipped with 17 sampling ports were filled with homogeneously contaminated aquifer material from a diesel fuel contaminated in situ bioremediation site. The columns were operated over 96 days at 12°C with artificial groundwater supplemented with O₂, NO₃⁻ and PO₄³⁻. Concentration profiles of O₂, NO₃⁻, NO₂⁻, dissolved inorganic and organic carbon (DIC and DOC, respectively), protein, microbial cells and total residual hydrocarbons were measured. Within the first 12 cm, corresponding to a mean groundwater residence time of < 3.6 h, a steep O₂ decrease from 4.6 to < 0.3 mg l⁻¹, denitrification, a production of DIC and DOC, high microbial cell numbers and a high removal of hydrocarbons were observed. Within a distance of 24 to 40.5 cm from the infiltration, O₂ was below 0.1 mg l⁻¹ and a denitrifying activity was found. In the presence and in the absence of O₂, n-alkanes were preferentially degraded compared to branched alkanes. The results demonstrate that: (1) infiltration of aerobic groundwater into columns filled with aquifer material contaminated with hydrocarbons leads to a rapid depletion of O₂; (2) O₂ and NO₃⁻ can serve as oxidants for the mineralization of hydrocarbons; and (3) the modelling of redox processes in aquifers has to consider denitrifying activity in presence of O₂.     

The characterization of water-soluble inorganic ions in PM2.5 during a winter period in Xi'an,China

The characteristics of water-soluble inorganic ions (WSIIs) during a winter period in a suburb of Xi'an, China, were investigated. Our results show that the total mass concentration of the dominant WSIIs (8) was 91.27 µg m^–3, accounting for 50.1% of the total mass concentration of PM_2.5 (particulates with a size of 2.5 µm or less). Secondary inorganic aerosols (SO₄^2?, NO₃^? and NH₄⁺) were the most abundant ions, accounting for up to 95.12% of the total ions. By using the anion and cation equivalence ratio method, PM_2.5 was shown to have weak alkalinity, and the chemical forms of WSIIs were mainly (NH₄)₂SO₄ and NH₄NO₃. The sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) suggested that larger proportions of SO₄^2? and NO₃^? were formed by gas-phase SO₂ and NO₂ in the sampling site. Ratio analysis also indicated that anthropogenic sources significantly contributed to WSII pollution. Among the anthropogenic sources, fixed pollution sources were found to be dominant over mobile sources.     

TiO2纳米管催化活性再生处理技术简

采用H₂O₂、Fe₂（SO₄）₃和Fenton溶液对失活的TiO₂纳米管进行再生处理，重点考察了3种溶液的浓度和处理时间等对再生效果的影响，初步分析了经处理后TiO₂纳米管催化活性得到再生或增强的机理。结果表明，经H₂O₂溶液处理后TiO₂催化活性能得到有效再生，经Fe₂（SO₄）₃和Fenton溶液处理后其催化活性不仅得到再生，还能显著增强，这与H₂O₂和Fenton的强氧化作用，及进入TiO₂纳米管的Fe³⁺的阻止电子-空穴对再复合作用有关。     

MnO2对煤粉中CaO固硫效率影响机理

采用热力学计算和实验方法对钙硫比n（CaO）/n（S）=2.0条件下不同钙基固硫剂的固硫效果进行了比较,发现：CaO的固硫效率最高。以CaO为固硫剂,研究了添加剂MnO2对CaO固硫效果的影响。结果表明,加入MnO2可以提高CaO的固硫效率,且其含量为1%时对CaO固硫的促进效果最佳。这是因为煤粉燃烧过程中MnO2将逐级分解,分解产物依次为Mn2O3和Mn3O4,锰的氧化物一方面可以催化CaO的固硫反应,另一方面,Mn3O4本身也参与到固硫反应之中,生成MnSO4,从而促进钙基固硫剂的固硫效果。     

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NOx photooxidation system

High concentrations (>15 μm³ cm^?3) of CaSO₄, Ca(NO₃)₂ and (NH₄)₂SO₄ were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO_x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO₄ and aqueous Ca(NO₃)₂), even at elevated concentrations. The presence of high concentrations of (NH₄)₂SO₄ aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH₄)₂SO₄ on SOA yield is found to be positively correlated with the (NH₄)₂SO₄ surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH₄)₂SO₄ seed aerosols.     

Reduction of sampling and analytical errors for electron microscopic analysis of atmospheric aerosols

Electron microscopy-energy dispersive spectroscopy (EM/EDS) can be used to determine the elemental composition of individual particles. However, the accuracy with which atmospheric particle compositions can be quantitatively determined is not well understood. In this work we explore sources of sampling and analytical bias and methods of reducing bias. Sulfuric acid [H₂SO₄] and ammonium sulfate [(NH₄)₂SO₄] particles were collected on beryllium, silicon, and carbon substrates with similar deposition densities. While [(NH₄)₂SO₄] particles were observed on all substrates, [H₂SO₄] and ammonia-treated [H₂SO₄] particles could not be found on beryllium substrates. Interactions between the substrate and sulfuric acid particles are implicated. When measured with EM/EDS, [H₂SO₄] particles exposed to ammonia overnight were found having lower beam damage rates (0.000 ± 0.002 fraction s⁻¹) than those without any treatment (0.023 ± 0.006 fraction s⁻¹) For laboratory-generated [C₁₀H₆(SO₃Na)₂] particles, the composition determined using the experimental k-factors evaluated from independent particle standards of similar composition and size shows an error less than 20% for all constituents, while greater than 78% errors were found when k-factors were calculated from the theory. This study suggests (1) that sulfate beam damage can be reduced by exposure of atmospheric particle samples to ammonia before analysis, (2) that beryllium is not a suitable substrate for atmospheric particle analysis, and (3) calibration (k-factor determination) using particle standards of similar size and composition to particles present in the atmosphere shows promise as a way of improving the accuracy of quantitative EM analysis.     

Selective Leaching of Valuable Metals from Waste Printed Circuit Boards

Abstract

This study was carried out to recover valuable metals from the printed circuit boards (PCBs) of waste computers. PCB samples were crushed to smaller than 1 mm by a shredder and initially separated into 30% conducting and 70% nonconducting materials by an electrostatic separator. The conducting materials, which contained the valuable metals, were then used as the feed material for magnetic separation, where it was found that 42% of the conducting materials were magnetic and 58% were nonmagnetic. Leaching of the nonmagnetic component using 2 M H₂SO₄ and 0.2 M H₂O₂ at 85 °C for 12 hr resulted in greater than 95% extraction of Cu, Fe, Zn, Ni, and Al. Au and Ag were extracted at 40 °C with a leaching solution of 0.2 M (NH₄)₂S₂O₃, 0.02 M CuSO₄, and 0.4 M NH₄OH, which resulted in recovery of more than 95% of the Au within 48 hr and 100% of the Ag within 24 hr. The residues were next reacted with a 2 M NaCl solution to leach out Pb, which took place within 2 hr at room temperature.