土壤环境中微塑料的污染现状及其影响研究进展

微塑料作为一种持久性污染物,对土壤生态系统具有严重影响,土壤中微塑料的污染已愈加受到国内外学者的广泛关注。当前关于土壤环境中微塑料的研究较少,针对当前土壤中微塑料的来源、分布、降解迁移、生态效应及污染防治等方面进行综述。主要包括以下几个方面:1）概括土壤生态系统中微塑料的来源、分布特点和迁移降解规律,确定了土壤环境中微塑料的赋存状态;2）总结土壤生态系统中微塑料与其他污染物的复合效应;3）分析了微塑料对土壤理化性质、动物、植物、微生物的影响,并揭示了微塑料对于土壤生态系统的影响;4）根据土壤微塑料的分布特点、降解迁移及生态效应提出污染防治措施。最后,对今后土壤微塑料的研究重点进行了展望。     

锐钛矿型二氧化钛的低温合成及其吸附除氟性能的研究

通过水解法在50℃低温条件下合成了锐钛矿型TiO₂,使用XRD、FT-IR、BET等方法对TiO₂进行了表征,并研究其对水中氟离子的吸附行为。结果表明:所合成锐钛矿型TiO₂比表面积达到278.93 m2/g,常温下对氟离子的最大吸附量为30.02 mg/g。吸附过程符合Langmuir等温线模型和准一级动力学模型,是自发性的吸热过程,吸附机理为静电吸引。     

Tuning the fill percentage in the hydrothermal synthesis process to increase catalyst performance for ozone decomposition

The performance of Ce-OMS-2 catalysts was improved by tuning the fill percentage in the hydrothermal synthesis process to increase the oxygen vacancy density. The Ce-OMS-2 samples were prepared with different fill percentages by means of a hydrothermal approach (i.e. 80%, 70%, 50% and 30%). Ce-OMS-2 with 80% fill percentage (Ce-OMS-2-80%) showed ozone conversion of 97%, and a lifetime experiment carried out for more than 20?days showed that the activity of the catalyst still remained satisfactorily high (91%). For Ce-OMS-2-80%, Mn ions in the framework as well as K ions in the tunnel sites were replaced by Ce⁴⁺, while for the others only Mn ions were replaced. O₂-TPD and H₂-TPR measurements proved that the Ce-OMS-2-80% catalyst possessed the greatest number of mobile surface oxygen species. XPS and XAFS showed that increasing the fill percentage can reduce the AOS of Mn and augment the amount of oxygen vacancies. The active sites, which accelerate the elimination of O₃, can be enriched by increasing the oxygen vacancies. These findings indicate that increasing ozone removal can be achieved by tuning the fill percentage in the hydrothermal synthesis process.     

Phosphate recovery with granular acid-activated neutralized red mud: Fixed-bed column performance and breakthrough curve modelling

Granular acid-activated neutralized red mud (AaN-RM) has been successfully prepared with good chemical stability and physical strength. However, its potential for industrial application remains unknown. Therefore, the performance of granular AaN-RM for phosphate recovery in a fixed-bed column was investigated. The results demonstrated that the phosphate adsorption performance of granular AaN-RM in a fixed-bed column was affected by various operational parameters, such as the bed depth, flow rate, initial solution pH and initial phosphate concentration. With the optimal empty-bed contact time (EBCT) of 24.27 min, the number of processed bed volumes and the phosphate adsorption capacity reached 496.95 and 84.80 mg/g, respectively. Then, the saturated fixed-bed column could be effectively regenerated with a 0.5 mol/L HCl solution. The desorption efficiency remained as high as 83.45% with a low weight loss of 3.57% in the fifth regeneration cycle. In addition, breakthrough curve modelling showed that a 5-9-1 feed-forward artificial neural network (ANN) could be effectively applied for the optimization of the fixed-bed adsorption system; the coefficient of determination (R²) and the root mean square error (RMSE) evaluated on the validation-testing data were 0.9987 and 0.0183, respectively. Therefore, granular AaN-RM fixed-bed adsorption exhibits promising potential for phosphate removal and recovery from polluted water.     

Acceleration of floc-water separation and floc reduction with magnetic nanoparticles during demulsification of complex waste cutting emulsions

Waste cutting emulsions are difficult to treat efficiently owing to their complex composition and stable emulsified structure. As an important treatment method for emulsions, chemical demulsification is faced with challenges such as low flocs–water separation rates and high sludge production. Hence, in this study, Fe₃O₄ magnetic nanoparticles (MNPs) were used to enhance chemical demulsification performance for treating waste cutting emulsions under a magnetic field. The addition of MNPs significantly decreased the time required to attain sludge–water separation and sludge compression equilibrium, from 210 to 20 min. In addition, the volume percentage of sludge produced at the equilibrium state was reduced from 45% to 10%. This excellent flocculation–separation performance was stable over a pH range of 3–11. The magnetization of the flocculants and oil droplets to form a flocculant–MNP–oil droplet composite, and the magnetic transfer of the composite were two key processes that enhanced the separation of cutting emulsions. Specifically, the interactions among MNPs, flocculants, and oil droplets were important in the magnetization process, which was controlled by the structures and properties of the three components. Under the magnetic field, the magnetized flocculant–MNP–oil droplet composites were considerably accelerated and separated from water, and the sludge was simultaneously compressed. Thus, this study expands the applicability of magnetic separation techniques in the treatment of complex waste cutting emulsions.     

干湿法结合工艺回收废弃SCR脱硝催化剂中的钛、钒和钨

利用干湿法结合工艺实现废弃SCR脱硝催化剂中Ti、V和W元素的高效分离和浸出,提出成套废弃SCR脱硝催化剂中Ti、V和W的回收技术。以废弃SCR脱硝催化剂为研究对象,优选Ti、V和W元素最佳浸出工况,研究硫酸溶解法回收TiO₂和有机萃取法回收V₂O₅和WO₃的回收率与纯度。结果表明:酸浸还原浸钒最优工艺条件为温度140℃,液固比30∶1;钠化焙烧浸钨最优工艺条件为煅烧温度750℃,反应物与Na₂CO₃配比（质量比）为1∶1.5,在以上条件下V、W浸出率分别达到97.6%、93.6%。利用硫酸溶解法回收得到的TiO₂产物主要以锐钛矿晶型存在形式,在最佳焙烧温度750℃下,TiO₂回收率达到97.17%,纯度为95.35%。利用有机萃取法回收得到的V₂O₅和WO₃产物的回收率和纯度分别为72.47%、75.43%和93.25%、78.26%。     

预处理对园林垃圾混合物料联合厌氧发酵的影响

采用超声、微波及碱热预处理技术强化园林垃圾、厨余垃圾与果蔬垃圾联合厌氧发酵产气性能,并以未进行预处理的实验组作为对照。结果表明:4组实验pH值在2 d内迅速降低至7.24~7.45,反应后期可稳定在7.7~8.0,表明厌氧消化系统有较强的稳定性。挥发性脂肪酸（volatile fatty acids,VFA）浓度在第2~4天内达到最大值。乙酸和丙酸是4组实验中VFA的主要成分,两者比例之和在70%以上。VFA浓度在第13天后降低到500 mg/L以下,且以乙酸为主。氨氮（TAN）浓度在前4 d内出现一定波动,随后逐渐升高至2190~2410 mg/L。游离氨氮（FAN）浓度呈先降低后增加趋势,并在第13天后逐渐趋于稳定,为144~209 mg/L。沼气中甲烷比例在第2天后均超过50%,并在第11~12天时达到最大值61.4%~63.8%。修正的Gomperts模型模拟结果表明:预处理技术可缩短反应体系厌氧产沼的适应时间,提高前期产气速率。除此之外,超声预处理与碱热预处理可显著提高基质甲烷产率,由未处理时的396 mL/g分别提高到601,536 mL/g,而微波预处理使得反应体系甲烷产量略有降低。     

电解锰渣基方沸石的制备及其对Pb2+的吸附性能

以电解锰渣为原料,经过"弱酸除杂-碱融活化-室温陈化-晶化"水热合成反应体系,在分别外加铝源和硅源的条件下制备方沸石ANA-A及ANA-S,运用XRF、XRD、SEM-EDS和BET等表征手段对2种方沸石的化学组成、晶相结构、微观形貌和比表面积进行分析。结果表明:在煅烧温度750℃、合成温度180℃、水热反应时间8 h的条件下,外加铝源和硅源均可合成方沸石。进一步研究2种沸石对水溶液中Pb2+的静态吸附性能,其所合成的电解锰渣基ANA-A及ANA-S方沸石均可以很好地用Langmuir等温模型拟合,属于单分子层吸附,饱和吸附量分别为161.29,185.19 mg/g,对初始浓度为100 mg/L的Pb2+去除率分别为93.69%和95.47%,且均符合Lagergren准二级动力学模型,属于化学吸附;两者中ANA-S的吸附效果更好。     

核桃壳生物炭对土壤中镉的钝化修复

通过室内模拟试验,研究了核桃壳生物炭（BC400、BC500、BC600）对人工Cd污染土壤（20 mg/kg）pH、Cd赋存形态分布的影响,并探究可能的修复机理。结果显示:经56 d修复后,与空白对照组相比,10%添加量的核桃壳生物炭BC400、BC500、BC600分别使土壤pH升高了1.07、1.31、1.38,弱酸可提取态Cd含量减少了17.02%、20.20%、24.53%,可还原态Cd含量减少了8.9%、19.1%、38.2%,可氧化态Cd含量增加了44.83%、78.45%、100%,残渣态Cd含量增加了66.03%、71.43%、89.21%。同时,土壤pH与土壤中弱酸可提取态Cd含量呈显著负相关（P<0.01）。综上,核桃壳生物炭能够对Cd污染土壤起到钝化修复作用。     

‘Emulsion locks’ for the containment of hydrocarbons during surfactant flushing

Reversible double water in oil in water (W/O/W) emulsions were developed to contain subsurface hydrocarbon spills during their remediation using surfactant flushing. Double emulsions were prepared by emulsifying CaCl₂ solutions in canola oil, and subsequently by emulsifying the W/O emulsions in aqueous sodium alginate solutions. The formation of double emulsions was confirmed with confocal and optical microscopy. The double emulsions reversed and gelled when mixed with the surfactants sodium dodecyl sulfate (SDS) and cocamidopropyl betaine (CPB). Gels can act as ‘emulsion locks’ to prevent spreading of the hydrocarbon plume from the areas treated with surfactant flushing, as shown in sand column tests. Shear rheology was used to quantify the viscoelastic moduli increase (gelation) upon mixing the double emulsion with SDS and CPB. SDS was more effective than CPB in gelling the double emulsions. CPB and SDS could adsorb at the interface between water and model hydrocarbons (toluene and motor oil), lowering the interfacial tension and rigidifying the interface (as shown with a Langmuir trough). Bottle tests and optical microscopy showed that SDS and CPB produced W/O and O/W emulsions, with either toluene or motor oil and water. The emulsification of motor oil and toluene in water with SDS and CPB facilitated their flow through sand columns and their recovery. Toluene recovery from sand columns was quantitated using Gas-Chromatography Mass-Spectroscopy (GC-MS). The data show that SDS and CPB can be used both for surfactant flushing and to trigger the gelation of ‘emulsion locks’. Ethanol also gelled the emulsions at 100 mL/L.