药渣生物炭基质联合麦饭石对土壤-黑麦草体系的调控与机制

以板蓝根药渣为原料,选择300℃和500℃厌氧裂解制备2种生物炭(BC300和BC500)、BC500载Fe改性炭(FeBC500)、天然麦饭石(MFS)、BC500与MFS等质量组合[BC500∶MFS(1∶1)]、Fe-BC500与MFS等质量组合[Fe-BC500∶MFS(1∶1)]材料为钝化剂,采用室内盆栽实验和等温吸附实验,研究了其对土壤-黑麦草体系的调控效果,并通过比表面孔分布测定(BET)、扫描电镜分析(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)探讨了其机制.结果表明,在添加量为2%(土)时,BC300、BC500、Fe-BC500、MFS、BC500∶MFS(1∶1)和Fe-BC500∶MFS(1∶1)均可显著降低(P 0. 05)黑麦草体内Cu和Cd含量以及显著增加黑麦草的生物量,且黑麦草的叶绿素含量和根系活力均可指示这一效果. BC300处理抑制黑麦草吸收Cu和Cd,增加黑麦草的生物量的效果要优于其他处理,可使黑麦草地下部分Cu和Cd含量分别减少44. 78%和63. 89%,地上部分分别减少76. 34%和53. 40%;地下部分生物量增加327. 22%,地上部分生物量增加504. 11%. Langmuir方程更好地拟合BC300、BC500和Fe-BC500的吸附效果,且对Cu的最大吸附量分别为8. 02、9. 20和8. 82 mg·g~(-1);对Cd的最大吸附量分别为7. 97、8. 51和7. 70 mg·g~(-1). Freundlich方程能更好地拟合MFS的吸附效果,对Cu和Cd的最大吸附量分别为7. 03 mg·g~(-1)和6. 10 mg·g~(-1). BC300和BC500主要通过其表面羟基、羧基、羰基和酯基,Fe-BC500主要通过其表面羟基和铁羟基,MFS主要通过其中Na Al Si3O8和Al2Si2O5(OH)4表面的硅羟基、羟基和羧基分别与Cu和Cd发生配合反应,进而达到钝化修复Cu和Cd污染土壤的效果.因此,药渣生物炭、铁改性药渣生物炭和麦饭石及其组合材料均可被用于Cu和Cd复合污染土壤修复,但修复机制不同.     

Polymer hydrogels with enhanced stability and heterogeneous Fenton activity in organic pollutant removal

Polymer hydrogel-based materials have been shown to act as novel Fenton catalysts for water treatment, but the rational design of hydrogel-based catalysts with good stability has been a great challenge. To increase the stability and activity of polymer-based Fenton catalysts, uniform urchin-like α-Fe_2O_3 was grown in situ in a PVA carrier matrix here. PVA molecules promoted the growth of urchin-like α-Fe_2O_3, and then the PVA hydrogel acted as a barrier and carrier to reduce agglomeration. Through coordination by hydroxyl groups,PVA had good combination with Fe ions and α-Fe_2O_3. The formation of Fe–O–C bonds between iron oxides and polymers was reported for the first time, enhancing the material stability during catalysis. Under higher PVA concentrations, the resulting composite hydrogel could generate more ˙OH due to the increase in the number of active sites because of the hairy urchin-like structure. In tetracycline degradation through a heterogeneous Fenton reaction, the resulting material had good catalytic activity from pH 2 to pH 10 with low iron leaching, good reusability and remained at a level of nearly 90%after five consecutive cycles. Density functional theory calculations were used to further prove the mechanism of structural change of the iron oxides. The HOMO and LUMO energies of the iron oxides changed from 5.428 and 4.899 eV to 5.926 and 5.310 eV,indicating that the presence of PVA could influence the charge of the iron atom. The results provide new insights into the preparation of polymer hydrogel-based heterogeneous Fenton catalysts with enhanced stability for water treatment.     

氯化石蜡产品中短链和中链同系物的指纹分布

使用气相色谱-电子捕获负化学电离质谱（GC-ECNI-MS）,对包含CP-42、CP-52和CP-70三种常见氯含量的22个CPs产品进行了测定,分析了不同氯含量的CPs产品中短链氯化石蜡（SCCPs）和中链氯化石蜡（MCCPs）同系物的分布模式.SCCPs同系物呈现5种分布特征,分别是CP-42型、三类CP-52型和CP-70型,MCCPs同系物呈现4种分布特征,分别是CP-42型和三类CP-52型,CP-70产品中MCCPs同系物未呈现出一致的分布规律.CPs生产原料石蜡中烷烃的成分组成和CPs生产工艺的不同,是造成产品同系物分布模式不一致的原因.通过统计学分析,得到CPs产品中SCCPs和MCCPs同系物的指纹分布,这是开展环境中CPs的源解析、迁移转化、归趋和毒性风险评价等研究的有利工具.     

One-step synthesis of Cu(II) metal–organic gel as recyclable material for rapid, efficient and size selective cationic dyes adsorption

Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic. Herein, a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG) with a nanoporous 3 D network structure prepared via a simple one-step mixing method was successfully employed for the removal of cationic dyes. The Cu-MOG exhibited high efficiency, with an adsorption capacity of up to 650.32 mg/g, and rapid adsorption efficiency, with the ability to adsorb 80% of Neutral Red within 1 min. The high adsorption efficiency was attributed to its large specific surface area, which enabled it to massively bind cationic dyes through electrostatic interaction, and a nanoporous structure that promoted intra-pore diffusion. Remarkably, the Cu-MOG displayed size-selective adsorption, based on adsorption studies concerning dyes of different sizes as calculated by density functional theory. Additionally, the adsorption performance of the Cu-MOG still maintained removal efficiency of 100% after three regeneration cycles. These results suggested that the Cu-MOG could be expected to be a promising and competitive candidate to conveniently process wastewater.     

Highly catalytic activity of Mn/SBA-15 catalysts for toluene combustion improved by adjusting the morphology of supports

Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in toluene oxidation. MnO_x supported on rod-like SBA-15(R-SBA-15) displayed the best catalytic activity and the conversion at 230°C reached more than 90%, which was higher than the other two catalysts. MnO_x species consisted of coexisting MnO_2 and Mn_2O_3 on the three kinds of SBA-15 samples. Large amounts of Mn_2O_3 species were formed on the surface and high oxygen mobility was obtained on MnO_x supported on R-SBA-15, according to the H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscopy(XPS) results. The Mn/R-SBA-15 catalyst with greater amounts of Mn_2O_3 species possessed a large amount of surface lattice oxygen, which accelerated the catalytic reaction rate. Therefore, the surface lattice oxygen and high oxygen mobility were critical factors on the catalytic activity of the Mn/R-SBA-15 catalyst.     

Ag/P-g-C3N4复合材料可见光催化降解双酚AF的机理研究

利用简单的热聚合及原位沉淀法制备了一系列不同质量比(1%～10%)的Ag/P-g-C_3N_4复合材料,采用XRD、SEM、TEM、UV-Vis DRS、FTIR、BET和XPS等表征手段对复合材料的形貌结构、光学特性和化学组成进行了表征.利用合成材料光催化降解双酚AF(BPAF),研究了溶液初始pH、溶解性有机质(DOM)对BPAF降解的影响,并对光催化降解机理进行了探讨.结果表明,在pH=7时,5%Ag/P-g-C_3N_4表现出最强的光催化性能,其在90 min内对BPAF的降解率达到100%.DOM在低浓度(0.5 mg·L~(-1))时促进了BPAF的光降解,而在高浓度时(2～10 mg·L~(-1))抑制了BPAF的光降解.活性基团捕获实验结果表明,在Ag/P-g-C_3N_4降解BPAF过程中,h~+和·OH起主要的作用,直接参与了BPAF的降解.相对于P-g-C_3N_4,Ag/P-g-C_3N_4光催化性能的增强主要是因为Ag的负载促进了e~-和h~+的分离,同时Ag单质的SPR效应提高了复合材料对可见光的吸收率,延长了光生载流子的寿命.     

中国水土资源本底匹配状况研究

论文以中国水资源二级区为基本单元,利用单位面积水资源量法和基尼系数法,以二级区水资源总量和潜在可开垦耕地面积为数据基础,评价中国水土资源本底匹配状况,为中国水土资源优化配置提供科学依据。首先根据适宜农作物耕种的高程、坡度和土壤类型条件,得到中国潜在可开垦耕地分布;然后,计算单位潜在可开垦耕地面积水资源量,评价中国水土资源本底匹配分布状况;最后,绘制水土资源洛伦兹曲线,计算基尼系数,对中国水土资源本底匹配总体状况进行评价。研究结果表明： 1）中国北部区域潜在可开垦耕地较多,西南部和南部沿海区域分布较少,未来具有较大耕地开发潜力的区域主要分布在北方; 2）中国本底水资源和潜在可开垦耕地资源空间分布存在严重错位; 3）较之已有研究成果中依据水资源量和耕地面积计算的基尼系数0.566,论文以本底水资源和潜在耕地为基础数据计算的基尼系数0.712要大很多,表征中国本底水土资源不匹配程度要严重得多,中国80%的水资源服务不到23%的潜在可开垦耕地。     

基于CSGD的排放清单处理工具研究

CSGD（crowd sourcing geographic data,众源地理数据）是通过互联网向大众或相关机构提供的一种开放地理空间数据,具有易获取、时效性好、准确性高等特点,在排放清单时空分配方面具有应用潜力.然而,现有排放清单处理工具不支持CSGD数据直接输入且难以满足排放清单空间分配和空气质量模式所需清单格式,因此,亟待开发一套可以拓展该类数据在排放清单领域应用的工具.以CSGD中的POI（城市设施兴趣点）数据为主要研究对象,基于QGIS平台、C++语言及Python语言,开发了在Windows系统下的ISAT（inventory spatial allocate tool,排放清单空间分配工具）工具及在Windows或Linux系统下的ISAT.M工具.结果表明:ISAT工具以POI数据为基础制作出的空间分配结果与排放源排放强度的空间分布特征的一致性较好;ISAT.M工具输出的inline清单可以作为CMAQ空气质量模式及其DDM敏感性分析模块的输入文件并开展模拟,通过与SMOKE模型的关闭源法模拟结果对比发现,二者在数据及空间分布上呈较好的一致性.研究显示,CSGD数据应用于排放清单空间分配可较好地反映排放源空间分布特征,同时由于此类数据存在信息冗杂、近郊区数据缺失等问题,在应用过程中应注意数据清洗及数据种类的选取工作.      

石家庄某制药企业污水处理过程中NH3排放研究

为了解污水处理过程中各处理单元NH₃的排放特征,采集石家庄某制药企业各污水处理单元以及经过废气治理后排放的样品,计算各采样点NH₃浓度及排放量。结果表明:各污水处理单元中,水解酸化池NH₃浓度和单位体积污水NH₃排放量均为最高,分别为62.89和3 360 mg∕m ³。各污水处理单元NH₃总排放量为0.97 kg∕h,单位体积污水NH₃排放量为9 312 mg∕m ³;经废气治理后,排入环境的NH₃为0.25 kg∕h,单位体积污水NH₃排放量为2 400 mg∕m ³,去除率为74.2%,经治理后NH₃排放量明显降低。南区、北区废气治理采用碱洗+氧化+水洗工艺,NH₃去除率分别为93.3%和83.1%;生物区废气治理采用生物滴滤床工艺,NH₃去除率为39.1%,碱洗+氧化+水洗工艺对NH₃的去除效果好于生物滴滤床工艺。     

基于二维和三维生态足迹的长三角城市群自然资本可持续性分析

城镇化和工业化进程的不断推进给城市群自然资本及其可持续利用带来较大的威胁。为明确城市群建设过程中自然资本可持续性变化特征,以长三角城市群为研究对象,采用二维和三维生态足迹评价模型,同时添加水资源账户对原模型进行改进以反映长三角地区水资源潜力与压力,研究分析了2005—2019年长三角城市群生态足迹、生态压力指数和生态协调指数变化、自然资本存量消耗和自然资本流量占用情况及其影响因素与作用机制。结果表明：1）研究期间,长三角城市群人均生态足迹和生态承载力分别为4.46和1.59 hm²/人,平均人均生态赤字为2.87 hm²/人,但万元GDP生态足迹不断下降,资源利用率不断上升;2）2005—2019年,长三角城市群生态压力指数由2.48升至3.25,生态协调指数由1.30变为1.25;3）基于改进三维生态足迹模型发现,长三角城市群资本存量利用程度越来越大,且对自然资本流量的更新起到较大抑制作用,2019年研究区自然资本存量的消耗量是资本流量占有量的2.26倍;4）影响因子分析表明,工业产值、能源消耗总量、建筑用地面积和城镇化率对生态足迹起到了正向促进作用,对自然资本的可持续性产生了较大压力。