模拟土壤淋洗废液中重金属的选择性去除与淋洗液的回收研究

土壤淋洗废液中污染物的选择性去除是实现淋洗液回收的关键.本文以硫化钠（Na₂S）、乙基黄原酸钾（PEX）、二甲基二硫代氨基甲酸钠（DTC）作为重金属沉淀剂处理电子垃圾污染土壤模拟淋洗废液,在筛选出Na₂S作为理想重金属沉淀剂的基础上,研究初始pH值、反应温度、沉淀剂浓度等因素对Na₂S分离络合态重金属的影响,并通过软件模拟和产物表征等方式推测反应机理.结果表明：Na₂S对柠檬酸络合态重金属的分离顺序依次为Cu、Pb、Cd,符合硫化物溶度积原则;反应温度、初始pH值对Na₂S处理络合态重金属无显著影响,重金属去除率均保持在90%以上,柠檬酸的回收率约为95%;Visual MINTEQ模拟结果显示,S^2-投加前液相中重金属主要以H₂CA^-、HCA^2-和CA^3-结合形式存在,S^2-投加后液相中重金属则以HS^-和S^2-结合形式存在;扫描电镜及能谱（SEM-EDS）表明,S^2-与金属阳离子按物质的量比1：1生成硫化物沉淀物,沉淀主要呈团聚、成簇和圆片状存在;X射线衍射（XRD）分析结果表明,沉淀产物中存在CuS、CdS、PbS和CuPbS₂.本研究结果可为化学沉淀法处理重金属污染土壤淋洗废液提供技术参考.     

色氨酸对生物成因铁硫酸盐次生矿物形成的影响

采用氧化亚铁硫杆菌催化合成铁硫酸盐次生矿物,研究不同L-色氨酸添加浓度对矿物合成体系pH、氧化还原电位（ORP）、Fe²⁺氧化率、总Fe沉淀率,以及次生矿物产量、化学组成及矿物相的影响.结果表明,随着体系色氨酸浓度的增加,pH降低幅度越小,ORP上升越不明显.色氨酸对铁硫酸盐次生矿物合成的影响依赖于其浓度,当色氨酸浓度低于1.67 g·L^-1时,色氨酸对铁硫酸盐次生矿物的形成起促进作用,表现为总Fe沉淀率及矿物产量随着色氨酸浓度升高而增加.而当色氨酸浓度升高至6.67 g·L^-1时,Fe²⁺氧化率、总Fe沉淀率和矿物产量远低于对照组,表明高浓度色氨酸会抑制铁硫酸盐次生矿物的形成.次生矿物内Fe/S比介于施氏矿物和黄钾铁矾的理论值之间,表明不同合成体系所得次生矿物均为黄钾铁矾和施氏矿物的混合物.矿物学特征分析表明,随着色氨酸浓度的升高,矿物的合成表现为黄钾铁矾向施氏矿物转移.     

裂解温度和离子强度对不同来源生物炭胶体释放行为的影响

近年来环境中生物炭胶体形成受到广泛关注,它是生物炭在环境中物理分解作用的重要过程,对污染物迁移有着重要影响.然而,目前对生物炭胶体释放过程和影响因素的研究甚少,人们对生物炭胶体释放机理的认识还很有限.本研究以小麦秸秆和花生壳为生物质来源,系统地探讨了生物炭的裂解温度（300~700 ℃）和溶液离子强度（0.1~10 mmol·L^-1）对生物炭胶体产率的影响.结果表明,随着裂解温度的升高,生物炭的耐磨性增强,且在较高的裂解温度下（≥500 ℃）花生壳生物炭的耐磨性显著强于小麦秸秆生物炭.生物炭的胶体产率受到生物质来源和裂解温度的显著影响,花生壳生物炭的胶体产率低于小麦秸秆生物炭,高温裂解（≥600 ℃）生物炭的胶体产率显著低于中低温裂解生物炭.在相同溶液离子强度下,生物炭胶体产率与其亚微米级碎片率呈显著正相关（p<0.05）,即生物炭中亚微米级碎片率越高,生物炭胶体产率越高.当溶液离子强度从1 mmol·L^-1增加到10 mmol·L^-1时,两种来源生物炭的胶体产率均显著降低,其降低的程度因生物炭裂解温度而异,其中低温裂解（300 ℃）生物炭的胶体产率降低了11.1%~11.2%,中高温裂解（≥ 500 ℃）生物炭的胶体产率降低了60.0%~97.2%.     

内质网应激在氟暴露致小鼠睾丸损伤中的作用

探讨了内质网应激在亚慢性氟暴露致小鼠睾丸损伤中的作用及分子机制.选用健康初断乳ICR雄性小鼠30只,随机分为对照组（C）、低氟组（LF）和高氟组（HF）,分别饮用自来水、5、30 mg·L^-1氟化钠水溶液90 d.亚慢性氟暴露结束后,以睾丸脏器系数、睾丸组织氧化/抗氧化酶和形态结构、精子质量、睾丸细胞凋亡、葡萄糖调节蛋白78（GRP78）、CCAAT/增强子结合蛋白同源蛋白（CHOP）、半胱氨酸天冬氨酸蛋白酶12（CASPASE-12）、半胱氨酸天冬氨酸蛋白酶3（CASPASE-3）为观测点.结果表明,与对照组比,LF组和HF组LDH、SOD、T-AOC活性下降,MDA含量上升,HF组GSH-PX活性下降,差异有统计学意义（p<0.05或p<0.01）;LF组可见细胞层次减少、间隙变大,成熟精子数量减少,HF组细胞溶解、层次紊乱,空泡化严重,少见成熟精子;LF组和HF组小鼠的精子活力降低,HF组小鼠精子数量下降,畸形率上升,差异有统计学意义（p<0.05或p<0.01）;LF组和HF组睾丸细胞凋亡指数上升,差异有统计学意义（p<0.01）;LF组和HF组Grp78、Caspase-12、Caspase-3基因表达水平上升,差异有统计学意义（p<0.05或p<0.01）.结果提示,除氧化应激以外,Caspase-12和Caspase-3基因表达异常可能是氟暴露致小鼠睾丸细胞凋亡异常的分子机制之一.     

基于AIS轨迹修复的船舶排放空间表征改进方法与应用

基于船舶自动识别系统（Automatic Identification System,AIS）数据表征船舶排放是目前船舶排放空间表征的主流方法,但AIS船舶轨迹点缺失会造成船舶排放量低估和船舶空间分布表征错误,进而影响船舶排放控制区的划分.为改进船舶排放空间表征,本研究以2013年广东省AIS船舶数据为例,采用基于时间和经纬度的三次样条方法对AIS船舶轨迹进行修复,结合动力法计算船舶排放,分析对比AIS轨迹修复前后船舶排放表征的差异,并利用空气质量模型和卫星观测评估AIS轨迹修复对船舶排放表征和广东沿海空气质量模拟的改进效果.结果表明：轨迹修复后广东省海域船舶轨迹点总数由4685773个增至5746664个,船舶NO_x排放量增加了0.6%.对于轨迹点与排放缺失集中的粤东海域,轨迹修复后船舶轨迹点数增加了88%,NO_x排放量在广东省船舶排放量的占比提升至22%,特别是在粤东重点修复海域NO_x排放量增加了2.7倍.原始轨迹在广东省海域较为稀疏,在粤东海域有明显轨迹缺失;轨迹修复后广东省海域船舶轨迹更为密集,粤东海域船舶轨迹得以补充,船舶排放空间分布更连贯.对比模拟结果与卫星观测结果,轨迹修复后粤东重点修复海域船舶模拟浓度与观测浓度的偏差由51%减至6%,总体上船舶排放模拟结果更接近卫星观测结果.     

金属改性对SAPO-34低温还原NO性能的影响

采用浸渍法制备金属改性SAPO-34分子筛催化剂,分析比较了不同单金属（Cu或Co）及不同比例双金属（Cu：Co=1：1、3：1、5：1,质量比）改性催化剂对NO的催化还原性能,评价了不同催化剂的N₂选择性,并采用扫描电子显微镜（SEM）、比表面积测试、X射线衍射分析（XRD）、NH₃-程序升温脱附（NH₃-TPD）等表征手段对催化剂的物化性能进行了分析.结果表明,单金属Cu改性催化剂具有较宽的温度区间,在250~450℃范围内NO的转化率始终保持在100%;双金属改性使NO转化率保持为100%的最低温度下降了25~50℃,显著拓宽了低温段窗口,其中,Cu₃Co₁/SAPO-34催化剂的低温催化还原性能最好,200℃即可实现100%的NO转化率,175℃下的转化率也高达80%以上.Cu-Co双金属改性SAPO-34分子筛催化剂具有优异的低温催化还原NO性能,具有在机动车尾气、工业废气的低温脱硝治理领域应用的潜力.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

Aerosol optical properties under different pollution levels in the Pearl River Delta (PRD) region of China

To clarify the aerosol hygroscopic growth and optical properties of the Pearl River Delta(PRD)region,integrated observations were conducted in Heshan City of Guangdong Province from October 19 to November 17,2014.The concentrations and chemical compositions of PM_(2.5),aerosol optical properties and meteorological parameters were measured.The mean value of PM_(2.5) increased from less than 35(excellent) to 35-75 μg/m~3(good) and then to greater than 75 μg/m~3(pollution),corresponding to mean PM_(2.5) values of 24.9,51.2,and 93.3 μg/m~3,respectively.The aerosol scattering hygroscopic growth factor(f(RH = 80%)) values were 2.0,2.12,and 2.18 for the excellent,good,and pollution levels,respectively.The atmospheric extinction coefficient(σext)and the absorption coefficient of aerosols(σ_(ap)) increased,and the single scattering albedo(SSA)decreased from the excellent to the pollution levels.For different air mass sources,under excellent and good levels,the land air mass from northern Heshan had lower f(RH) and σ_(sp) values.In addition,the mixed aerosol from the sea and coastal cities had lower f(RH) and showed that the local sources of coastal cities have higher scattering characteristics in pollution periods.     

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.     

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.