Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

•Addition of hindered amine increased thermal stability and viscosity of TTTM. •Addition of hindered amine improved the CO₂ absorption performance of TTTM. •Good the CO₂ absorption of recycled solvents after two regenerations. •Important role of amine group in CO₂ absorption of TTTM confirmed by DFT analysis. Is it possible to improve CO₂ solubility in potassium carbonate (K₂CO₃)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (ΔG*, ΔH*, and ΔS*). The CO₂ solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO₂ solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO₂ mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM+ CO₂ system has higher interaction energy (|ΔE |) than the TTM+ CO₂ system indicating the higher CO₂ affinity of the former system. This study might help scientists to better understand and to improve CO₂ solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD.     

煤矸石在新型动态循环淋溶装置中的淋溶特性

采用新型循环淋溶装置对煤矸石进行连续240h的淋溶实验,研究了煤矸石中重金属在淋溶过程中的溶出规律,通过向淋溶液中添加聚丙烯酰胺（CPAM）考察了固体颗粒物的沉降特性.结果表明： 随着淋溶反应时间延长,煤矸石中碱金属Na元素溶于水,形成碱性溶液,这两种因素导致淋溶反应初期淋溶液pH值升高.As、Zn离子浓度在淋溶时间为1~24h时呈上升趋势,而在24~72h,离子浓度呈下降趋势.淋溶液中Cr、Pb、Ba离子浓度在120h内均呈现上升趋势,而在120~240h,对于Cr离子来说,淋溶液的碱性环境促使Cr离子溶出率增大,但取样次数的增多也对Cr离子的浓度降低起到促进作用;淋溶液稀释和Ba离子的沉淀化合物形成,导致淋溶液中Ba离子浓度降低.120~240h,淋溶液中有机物被微生物的生化作用分解以及取样后外加塌陷区水体对淋溶液中COD和BOD起到稀释作用,使COD和BOD降低.在淋溶反应24h内,淋溶液中TON和NH₃-N出现波浪式变化,淋溶时间大于24h时,TON和NH₃-N总体呈升高趋势.随着淋溶时间延长,淋溶液中的固体颗粒物沉降速度逐渐变慢,延长了沉降时间.煤矸石中一些含氮化合物溶解于水中,使淋溶液中电离出 NH₄⁺离子,形成碱性环境.     

基于PBPK模型的大鼠体内镉分布的比较:联合暴露及单独暴露

环境中同时存在着多种重金属元素,联合暴露与单独暴露时,重金属在体内的蓄积分布情况也可能有所差异。为探究重金属元素(汞、铬、砷、铅)对镉(Cd)在体内分布的影响,建立了大鼠在Cd暴露下的药代动力学(PBPK)模型,并进行了包括Cd在内5种重金属的联合毒性实验,比较了Cd单独给药与重金属混合物给药2种方式下大鼠肝脏、肾脏中的Cd浓度水平。结果表明,联合暴露高(Hg Cl23.67 mg·kg~(-1),NaAsO_2 3.67 mg·kg~(-1),CdCl_2 10.55 mg·kg~(-1),K_2Cr_2O_7 6.40 mg·kg~(-1),Pb(OOCCH_3)_2·3H_2O 133.33 mg·kg~(-1))、中(HgCl_20.367 mg·kg~(-1),NaAsO_2 0.367 mg·kg~(-1),CdCl_2 1.055 mg·kg~(-1),K2Cr2O70.640 mg·kg~(-1),Pb(OOCCH_3)_2·3H_2O 13.333 mg·kg~(-1))、低(HgCl_2 0.0367 mg·kg~(-1),Na As O20.0367 mg·kg~(-1),Cd Cl20.1055 mg·kg~(-1),K_2Cr_2O_7 0.0640 mg·kg~(-1),Pb(OOCCH3)2·3H2O 1.3333 mg·kg~(-1))剂量组大鼠肝脏中Cd浓度分别为13.37、0.78和0.06μg·g~(-1);肾脏中Cd浓度分别为14.41、1.64和0.15μg·g~(-1)。与对照组相比,暴露组中Cd浓度有显著升高,且不同剂量组之间均有显著性差异。同剂量Cd单独暴露的PBPK模拟结果显示,肝脏及肾脏中的Cd浓度水平落在联合毒性实验结果的浓度范围内,初步推断其他4种重金属的联合暴露并没有影响Cd在大鼠肾脏和肝脏中的浓度分布。     

Characteristics of the stabilized/solidified municipal solid wastes incineration fly ash and the leaching behavior of Cr and Pb

Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure.     

生物炭对菜地土壤氮平衡及酸碱缓冲能力的影响

针对太湖地区菜地化肥氮投入量较大导致氮淋失严重及土壤酸化的现状,选取太湖地区的菜地土壤,利用盆栽试验连续种植三季小白菜,结合生物炭埋袋回收技术,研究不同化肥氮施用量(以N计,0和110 mg/kg)及生物炭添加量(w为0%、1%、2%和5%)对土壤氮淋失及酸碱缓冲能力的影响. 结果表明:在化肥氮施用量为110 mg/kg条件下,与无生物炭添加相比,生物炭添加量为2%时可使作物对土壤矿质态氮的利用效率提高约1倍(由41%增至81%),因化肥氮施用引起的土壤氮素残留量降低83%;生物炭添加可有效减少48%~65%的土壤氮淋失量,当添加量为1%、2%时,生物炭主要通过削减淋失液中ρ(TN)来降低土壤氮淋失量;添加量为5%时,则主要通过削减淋失液体积来实现. 无论是否添加化肥氮,生物炭均能有效维持土壤原有的pH、w(有机质)及w(盐基离子);促使土壤酸碱缓冲能容量增加22%~37%,致酸速率降低17%~80%,显著提升了土壤的酸碱缓冲能力. 研究显示,在化肥氮施用量为110 mg/kg条件下,生物炭添加量为2%时能对土壤酸化产生较好的缓冲效果.      

森林植被对降水水化学的影响

综述了森林植被各个层次对降水水化学影响的主要研究成果,并指出了目前该方面研究存在的问题及今后需要努力的方向。大量集中在乔木层的研究表明,与林外雨比较,穿透雨、树干茎流中多数元素的浓度均呈增加的趋势,浓度大小的总趋势为树干茎流>穿透雨>林外降雨,K、Mg、Mn等表现突出,浓度可增加10倍以上;影响元素浓度变化因素包括降水特征、林分类型、大气状况等;具体到某一种元素,不同区域、不同林型间研究结果差异很大,很难得出一致的结论。对灌草层和枯落物层吸附淋溶作用研究较少,也就不能正确评价森林植被对降水水化学的综合效应。因此,在空间尺度上,要加强不同区域森林植被各个层次的研究;在时间尺度上,短时间的观测缺乏代表性,长期定位观测更具科学性。此外,目前的研究,尤其是国内的研究,只是对现象的揭示,缺乏过程及机理的深入研究,限制了我们对森林植被的内在运行机制和客观规律的正确认识。     

基于PLIF的混合气温度和浓度测量及其应用

缸内混合气温度和浓度分布,对发动机稳定运行,保障行车安全、避免发生路上人身伤亡或财物损失有重要影响。为了测量发动机缸内混合气的温度和浓度分布,建立了利用单波长激光诱导双示踪剂产生双荧光的测试系统,并拍摄了不同混合气温度、压力和浓度下的荧光图像,获得了不同示踪剂的荧光强度及其比值随温度、压力和浓度的变化关系,并将标定结果用于光学发动机缸内混合气的温度和浓度测量。结果表明,荧光强度及荧光比值均受到环境的压力、温度和混合气浓度的影响。利用PLIF方法得到的片光源穿过的缸内水平截面内的平均温度与用气缸压力计算的同一曲轴转角下的缸内平均温度变化趋势相同,两者之间的差值随着活塞上行而逐步减小。     

典型电子废物中多溴联苯醚的模拟浸出释放特征

选取废旧打印机外壳为典型电子废物,以商用腐殖酸溶液为浸提剂,采用浸出试验,模拟研究了废旧打印机外壳中PBDEs(多溴联苯醚)在简易填埋或与生活垃圾共处置场景下,在不同废物粒径、浸提剂DOC浓度、pH、浸提时间和液固比下的浸出特征. 分别用索氏提取法和液液萃取法提取废旧打印机外壳及其浸出液中的PBDEs,采用气相色谱-质谱法(GC-MS)对11种PBDEs同系物的浓度进行定性、定量检测. 结果表明,废旧打印机外壳中BDE28、BDE47、BDE66、BDE85、BDE99、BDE100、BDE153、BDE154被检出,而在浸出液中仅有BDE28、BDE47、BDE66、BDE85、BDE99、BDE153被检出,∑₆PBDEs的浸出率仅为0.04%~0.44%;垃圾渗滤液和土壤溶液中DOM可以促进废旧打印机外壳中PBDEs的浸出,随着浸提剂ρ(DOC)的增大,PBDEs的浸出量增加;在酸性条件下PBDEs的浸出量低于在中性条件下的浸出量;随着浸出时间的延长,PBDEs的浸出量不断增加,但在试验设定的480h内,没有得到一个液固体系的平衡时间,可见废旧打印机外壳中PBDEs的浸出是一个缓慢释放的过程.      

辽河表层沉积物重金属生态风险与综合毒性表征

采用ICP-MS测定了辽河26个支流表层沉积物间隙水中7种重金属(Pb、Cu、Cr、Zn、Ni、As、Cd)的含量,并应用间隙水毒性基准单位(IWCTU)和Nemeraw指数(NI)对间隙水重金属生态风险进行了评价;同时利用摇蚊幼虫活体生物毒性测试方法评估了辽河流域26个支流表层沉积物的综合毒性。研究结果显示,辽河支流表层沉积物间隙水7种重金属平均含量为:Pb 3.92μg·L-1,Cu 5.73μg·L-1,Cr 7.21μg·L-1,Zn 4.33μg·L-1,Ni 4.48μg·L-1,As 5.89μg·L-1,Cd 0.29μg·L-1,根据IWCTU值和NI值,柴河、养息牧、亮子河、凡河、付家窝堡、接官厅具有潜在的生态风险;综合毒性表征结果表明,柴河、长沟子河、付家窝堡、柳河、一统河、潮沟河表层沉积物对摇蚊幼虫具有较高毒性。结合重金属毒性和综合毒性分析,认为辽河流域支流表层沉积物毒性应该是由复合污染形成,而不仅仅是重金属污染。     

Limiting explosible concentration of hydrogen–oxygen–helium mixtures related to the practical operational case

This paper presents data on the limiting (minimum) concentrations of hydrogen in oxygen, in the presence of added helium, at elevated temperature and pressure related to the practical operational case. A 5 L explosion vessel, an ignition sub-system and a transient pressure measurement sub-system were used. Through a series of experiments carried out using this system, the limiting concentrations of hydrogen in oxygen and helium at different initial pressures and temperatures for the practical operational case were studied, and the influence of ignition energy and initial temperature on the limiting concentration of hydrogen in oxygen and helium was analyzed and discussed. The variation of ignition energy within the studied range is found to have a significant effect on the limiting concentration of hydrogen in oxygen and helium at lower initial temperature. However, when the ignition energy is higher than 32 mJ, the limiting hydrogen concentration remains almost changeless as the initial temperature increases from 21 °C to 90 °C. The limiting explosible concentration of hydrogen–oxygen–helium mixture decreases as the ignition energy increases when the initial temperature is lower. When the initial temperature is higher, the ignition energy has little effect on the limiting hydrogen concentration of hydrogen–oxygen–helium mixtures. When the initial temperature reaches 90 °C, the limiting hydrogen concentration remains almost changeless with an increase in ignition energy. The limiting explosible concentration of hydrogen in the mixtures, at the initial temperature of 21 °C and the ignition energy of 0.5 mJ, is 8.5% and that of oxygen is 11.25%.