Ca(OH)2解吸并固定混合吸收液中CO2的实验研究

CO₂化学吸收法分离纯度高,技术成熟,但能耗过高及成本是困扰该技术发展的瓶颈.在常压条件下对利用Ca（OH）₂直接矿物碳酸化固定MDEA/PZ混合吸收富液中CO₂进行了一系列实验研究,考察了吸收液负荷、Ca（OH）₂投加量、pH、温度及搅拌速率等因素对解吸率的影响,并利用动态吸收-解吸循环实验研究了其CO₂吸收性能和循环使用稳定性,最后对碳酸化反应产物进行了XRD、TEM分析.结果表明,在常压条件下,Ca（OH）₂可以通过液相直接矿物碳酸化对CO₂进行直接固定,并实现吸收富液的再生;随着负荷的升高及Ca（OH）₂投加量、pH、搅拌速率的增大,解吸率随之增加;随着溶液温度升高,解吸率下降;经过5次动态吸收-解吸循环实验后CO₂吸收量可以达到并保持在0.57 mol·L^-1,显示出了良好的循环稳定性.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

餐厨垃圾生物有机肥对贫瘠黄褐土改良的研究

为了阐明餐厨垃圾生物有机肥改良贫瘠土壤的作用机制,以贫瘠黄褐土为研究对象,通过不施肥、长期（>5 a）施用化肥、中长期（5 a）施用少量餐厨垃圾生物有机肥和短期（1 a）施用大量餐厨垃圾生物有机肥4种施肥方式,分别记为CK组、CF组、LOF-5组和MOF-1组,对比分析不同施肥方式对土壤OM（有机质）、活性有机碳、营养元素和团聚体等的影响.结果表明:①施用餐厨垃圾生物有机肥可显著提高土壤OM、活性有机碳含量,其中,MOF-1组提高效果最显著,与CK组相比,w（OM）可提高173.29%,w（ROC）（ROC为易氧化有机碳）增加了39.17%,w（POC）（POC为颗粒有机碳）和w（DOC）（DOC为可溶性有机碳）分别是CK组的13.85和10.32倍.②中长期（5 a）施用少量餐厨垃圾生物有机肥可增加土壤中较大粒径团聚体的占比,且更有利于提高土壤团粒结构的稳定性,LOF-5组>2 mm粒级的团聚体占比是CK组的4.68倍;与CK组相比,LOF-5组MWD（平均重量直径）增加了100.00%,GMD（几何平均直径）增加了82.98%,>0.25 mm水稳定性团聚体质量占比（DR_0.25）增加了27.20%.③中长期（5 a）施用少量餐厨垃圾生物有机肥可增加土壤中w（TN）（TN为全氮）和w（AN）（AN为速效氮）,与CK组相比,LOF-5组w（TN）和w（AN）分别增加了77.42%和20.82%.施用餐厨垃圾有机肥也可同时增加土壤中w（AP）（AP为速效磷）和w（AK）（AK为速效钾）,MOF-1组增加效果较佳,w（AP）和w（AK）分别是CK组的9.43和3.39倍.研究显示,中长期（5 a）施用少量餐厨垃圾生物有机肥可提升土壤固碳能力,提高土壤养分利用的有效性,从而提升耕地土壤质量,减少化肥施用量,是我国贫瘠黄褐土改良的有效施肥模式.      

微生物菌剂对堆肥功能微生物重构的影响

堆肥产品不仅可以作为有机肥或土壤改良剂,还可以在包气带土层防护地下水污染的过程中起到微生物载体的作用.在堆肥中接种菌剂能够加速堆肥进程,促进堆肥材料的腐熟,但是也有研究认为接种剂与堆肥土著微生物的竞争会导致菌剂无法发挥作用.为了阐明菌剂与土著微生物之间的相互作用,采用宏蛋白质组学方法,分析餐厨垃圾堆肥接菌组（木质纤维素混合菌剂）和对照组（未接菌）中功能微生物群落和碳水化合物代谢途径的变化.结果表明:接菌组中假单胞菌目（Pseudomonadales）和散囊菌纲（Eurotiomycetes）菌群的相对丰度比对照组分别提高了12.5%和22.0%,成为优势细菌和真菌,二者在碳水化合物代谢活性上也成为优势菌群.菌剂主要是由芽孢杆菌目（Bacillales）和散囊菌纲的曲霉（Aspergillus）组成,曲霉因具有堆肥系统所需的木质纤维素分解能力而成为优势真菌,而菌剂中的芽孢杆菌虽然数量较多,但是缺乏堆肥系统所需的功能而无法成为优势细菌.餐厨垃圾中易降解物质分解过程中产生的有机酸会导致酸性环境,对照组中能够适应酸性环境的芽孢杆菌目和酵母菌纲（Saccharomycetes）是优势群落,添加菌剂后,堆肥系统中土著的假单胞菌目和散囊菌纲具有较高的碳水化合物代谢活性和多种有机酸转化通路,因此在与菌剂中的芽孢杆菌目和土著的芽孢杆菌及酵母菌的竞争中成为优势菌群.研究显示,外源菌剂与土著微生物之间以及各土著微生物之间都会发生竞争作用,能否成为优势菌群取决于是否适应堆肥底物新陈代谢的变化,因此只要选择好菌剂的功能和接种时机,菌剂就能够发挥原有的作用.      

生物炭复合青霉菌修复砷污染土壤对其微生物群落功能多样性的影响

真菌修复砷污染土壤是一种能够有效吸附固化环境中砷的重要措施.生物炭作为目前修复重金属的热点,其多空疏松的结构、较高的离子交换量、丰富的有机碳含量等都说明了其在土壤修复中的地位.为了探究生物炭与青霉菌在修复砷污染土壤的同时对土壤中微生物活性及其多样性的影响,在室内孵育条件下,运用Biolog法研究了3×3随机区组试验（3个生物炭梯度分别为0%、2%、4%,3个青霉菌梯度分别为0%、10%、20%）下土壤微生物对不同类型碳源的利用能力以及多种功能性指数的影响.结果表明:①添加青霉菌与生物炭后,土壤中有效砷含量较对照组显著下降,从而影响其微生物群落功能多样性.②砷污染土壤中微生物群落功能多样性、碳源利用丰富度随生物炭浓度梯度的升高呈先升后降的趋势.③高接菌量（20%）与低接菌量（10%）对砷污染土壤中微生物群落功能多样性的影响没有显著性差异.④2%生物炭与10%青霉菌处理土壤中微生物群落功能多样性、碳源利用丰度最高.⑤青霉菌对胺类及少部分酸类碳源的利用能力较弱（AWCD < 0.5,AWCD为Biolog微平板孔中溶液吸光值平均颜色变化率）,对氨基酸类中大部分碳源以及脂类碳源的代谢能力较强（AWCD>1.0）,对糖类、酚酸类的代谢能力稍弱（AWCD为0.3~1.0）,青霉菌对D-半乳糖醛酸、L-天冬酰胺酸、L-丝氨酸、L-精氨酸、r-羟基丁酸这5种碳源的利用率最高（AWCD>1.2）.研究显示,低浓度生物炭可增加砷污染土壤中微生物群落多样性,生物炭含量的继续增加会对微生物产生抑制作用;青霉菌添加到砷污染土壤后,会显著提升砷污染土壤中微生物的群落功能多样性,改善砷污染土壤中微生的物群落结构;青霉菌的优势碳源大多为植物根系分泌物,可为后续青霉菌与超积累植物复合修复砷污染土壤提供参考.      

过硫酸钠缓释材料的释放性能及其对2, 4-二硝基甲苯的降解效果

针对原位化学氧化技术修复土壤和地下水时氧化剂因释放过快而导致的利用率低等问题,通过熔化成型法制备过硫酸钠缓释材料,分析石蜡、硅砂和过硫酸钠不同配比对材料成型度和释放性能的影响,研究缓释过程中溶液pH的变化,探讨其在水溶液中的缓释行为及其对2,4-二硝基甲苯（2,4-DNT）的降解效果.结果表明:当固定过硫酸钠质量为6 g、硅砂质量为18 g、蜡砂比（石蜡、硅砂质量之比）为1:4~1:8时,过硫酸钠缓释材料成型度适中,且过硫酸钠的累积缓释量随着时间的延长而逐渐增大,第31天时过硫酸钠累积释放百分比为74.67%~88.40%,可实现过硫酸钠的持续可控释放.当硅砂质量为18 g、蜡砂比为1:1~1:6时,过硫酸钠累积释放百分比随着过硫酸钠质量的增加而增大,且溶液中的pH呈先降低后上升的变化规律.缓释材料缓释前后实物图和显微镜分析结果显示,过硫酸钠缓释材料的释放是一个由外到内、速率由快变慢最终趋于平稳的过程.过硫酸钠质量为12 g、硅砂质量为18 g、蜡砂比为1:4的缓释材料对2,4-DNT具有较好的降解效果,第16次置换浓度为0.2 mg/L的2,4-DNT水溶液时,2,4-DNT的降解率为56.38%.研究显示,改变制备材料的配比可有效实现缓释材料中过硫酸钠的缓慢释放及对污染物的有效降解,可为原位化学氧化修复土壤和地下水提供理论支撑.      

尕海湿地植被退化过程中有机碳及相关土壤酶活性变化特征

以青藏高原东缘尕海湿地不同植被退化程度样地为研究对象,采用定位研究与室内试验相结合的方法,研究植被退化过程对土壤有机碳和土壤酶活性的影响。结果表明：植被退化显著影响土壤有机碳含量和土壤酶活性,降低了土壤有机碳的含量和酶促反应效率,且这种影响随土层深度变化有所不同。四种植被退化阶段有机碳含量和酶活性均值总体上（0~100 cm）表现为未退化>轻度退化>中度退化>重度退化。不同土层中,20~40 cm土层的有机碳含量中度退化>轻度退化;0~10 cm土层中淀粉酶和纤二糖酶中度退化阶段活性值较高;20~100 cm土层中蔗糖酶重度退化阶段活性值最高,纤二糖酶活性重度退化>中度退化。同一退化程度土壤有机碳含量、蔗糖酶和纤二糖酶活性随土层深度增加显著降低（P<0.05）;淀粉酶和纤维素酶活性在>40 cm土层中活性值有所上升,整体呈波动下降趋势。     

珠江口夏季海陆源有机碳的模拟研究——分布特征、贡献比重及其迁移转化过程

基于经过验证的三维水动力-水质模型,对珠江口夏季有机碳进行海陆源区分,并对海陆源有机碳的分布特征、贡献比重及其通量过程进行研究.结果表明,水平方向上,珠江口夏季陆源（海源）有机碳浓度从口门到外海逐渐降低（升高）,在表、底层海水中平均浓度分别为1.45和0.87mg/L（0.97和1.05mg/L）;垂直方向上,在层化水域陆源（海源）有机碳浓度从上到下逐渐递减（升高）,在非层化水域海陆源有机碳浓度垂向分布较为均匀.珠江口夏季海源有机碳贡献率表层海水低于底层海水,平均贡献率为48.26%,沿向海方向海源有机碳贡献率逐渐增加--从内伶仃洋水域的4.43%逐渐提升到外伶仃洋东侧水域的81.20%.珠江口水动力条件复杂,在径流、潮汐、季风等因素的作用下陆源有机碳向海输送且向海输送量逐渐递减;海源有机碳在不同水域动力输送特征不同,西南水域向海输送,向海输送量逐渐递增;东北水域向岸输送,向岸输送量逐渐递减.陆源有机碳生化反应活性较弱,只有小部分被生化过程消耗,其迁移转化主要由沉降过程控制,而海源有机碳的迁移转化,则由口门的动力输送过程主控向外海的生化耗碳过程主控过渡.此外,海源有机碳沉降作用明显低于陆源有机碳,生化作用明显高于陆源有机碳.