人类活动对漓江地表水体水-岩作用的影响

人类活动对流域水质的影响受到越来越多的关注.为探讨人类活动对岩溶地表水体水-岩作用的影响,以受农业、工业、旅游业活动及城市发展综合影响的漓江流域为研究对象,于2016年7~11月采集河水样,分析水化学和δ~(13)C_(DIC)数据.结果表明:(1)漓江水化学类型为HCO_3-Ca.在阴离子成分中,SO_4~2和NO_3~-仅次于HCO_3~-,并且在漓江桂林至阳朔段,因城市及城镇分布密集,旅游业发达,浓度较高.(2)[Ca~(2+)+Mg~(2+)]/[HCO_3~-]当量比值在1.01~1.51之间,[Ca~(2+)+Mg~(2+)]/[SO_4~(2-)+NO_3~-+HCO_3~-]比值在0.85~1.12之间,说明硫酸、硝酸参与了水-岩作用.(3)碳酸溶蚀碳酸盐岩的比例平均为75.89%.硫酸和硝酸溶蚀碳酸盐岩的比例平均为24.11%.硝酸、硫酸溶蚀碳酸盐岩的能力多雨期强于少雨期.此外,硫酸和硝酸溶蚀碳酸盐岩的比例从上游到下游呈波动增大趋势,最高值出现于灵川县城,最低出现于漓江上游的华江.(4)碳酸风化碳酸盐岩对HCO_3~-的贡献最大,平均为83.58%;其次为硫酸和硝酸风化碳酸盐岩,平均为14.24%;碳酸风化硅酸盐岩对HCO_3~-的贡献最小,平均为2.18%,华江和峡背碳酸风化硅酸盐岩对HCO_3~-的贡献较其他点突出,这与流域地质背景相符合.(5)δ~(13)C_(DIC)值介于-11.95‰~-7.61‰之间;通过端元混合模型估算的δ~(13)C_(DIC-rock)介于-14.24‰~-7.23‰之间.多雨期δ~(13)C_(DIC)值与δ~(13)C_(DIC-rock)值比较接近,少雨期δ~(13)C_(DIC)值明显重于δ~(13)C_(DIC-rock).δ~(13)C_(DIC)与δ~(13)C_(DIC-rock)之间存在一定差异,是由于受到水生植物光合作用的影响.     

利用含Cu(Ⅱ)废水强化微生物燃料电池处理含Cr(Ⅵ)废水

采用双室微生物燃料电池(MFC)反应器,考察了不同Cr(Ⅵ)/Cu(Ⅱ)浓度配比和外电阻条件下添加Cu(Ⅱ)对MFC阴极去铬的影响.结果表明,MFC阴极处理Cr(Ⅵ)废水时,添加一定浓度的Cu(Ⅱ)废水能提高MFC阴极去铬的效率,且添加Cu(Ⅱ)的浓度越高,提高的效果越明显.在所设置外电阻(10、500、1 000、2 000Ω)条件下,随着外电阻的降低,Cu(Ⅱ)对MFC阴极去铬的强化作用越明显.最终在Cr(Ⅵ)/Cu(Ⅱ)质量浓度配比1∶4,外电阻10Ω时,MFC阴极Cr(Ⅵ)的去除率达91.00%,较单独去铬时(39.13%)提高了132.57%.对反应后的电极进行扫描电镜附加能谱分析及X射线光电子能谱分析表明,Cr(Ⅵ)在阴极的还原产物为不导电Cr_2O_3,其附着于电极表面引起电极导电性能下降,而添加Cu(Ⅱ)后其在阴极还原为Cu和Cu_2O,该产物则在一定程度上提高了电极导电性能,缓解Cr_2O_3沉积造成的阴极钝化,从而强化了MFC阴极去铬的效率.     

浒苔生物炭的特征及其对Cr(Ⅵ)的吸附特点和吸附机制

为使浒苔得到资源化利用,本研究采用慢速热解技术于不同温度下制备浒苔生物炭,并对其理化性质进行表征.结果表明,400℃时,浒苔裂解已达较高程度.浒苔生物炭产率及灰分含量与热解温度呈负相关,碳含量与热解温度呈正相关,其表面呈蜂窝状多孔结构,比表面积为44.54~317.82 m~2·g~(-1),表面含有丰富的羟基(—OH)和羧基(—COOH)等含氧官能团.吸附实验显示,浒苔生物炭对Cr(Ⅵ)的吸附符合准二级动力学方程和Langmuir等温吸附模型.表明浒苔生物炭对Cr(Ⅵ)的吸附为单分子层化学吸附,主要受快速反应过程控制.浒苔生物炭吸附Cr(Ⅵ)的最适p H为2,吸附容量表现为BC400BC700BC600BC500BC300,其中BC400的吸附量为4.79 mg·g~(-1).浒苔生物炭对Cr(Ⅵ)的吸附机制主要包括生物炭与HCr O-4和Cr2O_2-7等阴离子之间的静电作用,以及生物炭表面—OH和—COOH等含氧官能团的络合作用.     

Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

AOD渣中铬的短期淋溶特性

在固体废弃物淋溶毒性测试标准的基础上,采用静态实验方法研究淋溶时间、固液比、溶解氧和溶液初始pH值对AOD渣中Cr的短期淋溶的影响。实验结果表明,AOD渣使淋溶液pH快速升高、E和DO快速降低;Cr淋溶呈现快淋溶和慢淋溶2个阶段,24 h内Cr淋溶基本达到平衡;尽管固液比对AOD渣淋溶液中Cr3+浓度的影响较小,但考虑到Cr3+与OH-间的平衡反应,直接采用固体废弃物淋溶毒性测试标准会低估Cr的淋溶量,从而过低评价Cr的淋溶毒性;短期淋溶过程中,溶解氧对Cr淋溶的影响相对较小;与中性淋溶液相比,碱性淋溶液对AOD渣中Cr的淋溶影响较小。而在酸性条件下,延长淋溶时间、降低溶液初始pH值将显著增加淋溶液中Cr3+的浓度。因此,采用中性淋溶液评价AOD中Cr淋溶毒性将显著低估Cr的淋溶毒性。     

ε-聚赖氨酸生产废菌体对六价铬吸附影响的研究

以ε-聚赖氨酸(ε-PL)发酵生产废菌体小白链霉菌(Streptomyces albulus)PD-1为研究对象,探讨了其对吸附Cr(Ⅵ)的影响.实验过程中,对预处理方式、pH、初始Cr(Ⅵ)浓度、吸附时间和温度等因素进行了考察.结果表明,HCl预处理的菌体具有较好的吸附能力,Cr(Ⅵ)的吸附增加率达到22.7%,最佳pH为2.0左右,温度对Cr(Ⅵ)的吸附影响不大.实验过程中分别采取Langmuir和Freundlich 2种吸附等温模型对实验数据进行了拟合,得到2个模型的线性相关系数R2分别为0.979 4和0.979 8,这表明吸附过程中既存在单层吸附同时也存在复杂的多层吸附,小白链霉菌对Cr(Ⅵ)的最大理论吸附量为23.92mg.g-1.通过傅里叶变换红外光谱分析,酰胺基和羟基等基团在吸附过程中起主要作用.     

Cr（Ⅵ）对海洋浮游植物生长的影响

采用一次培养实验方法,研究了Cr（Ⅵ）污染物对海洋浮游植物生长的影响.结果表明高浓度Cr（Ⅵ）对8种浮游植物的生长普遍有抑制作用,而较低浓度Cr（Ⅵ）则易促进旋链角毛藻、青岛大扁藻及中肋骨条藻的生长.并且在Logistic生长模型的基础上结合Lorentz方程和GaussAmp方程,引入Cr（Ⅵ）污染物浓度项,建立Cr（Ⅵ）污染物条件下海洋浮游植物生长动力学模型,来描述Cr（Ⅵ）存在条件下海洋浮游植物的生长过程,其中Lorentz方程可描述Cr（Ⅵ）浓度的变化对浮游植物生长速率参数的影响,而GaussAm     

铁氧化物改性黏土对Cr(Ⅵ)的吸附性能研究

利用铁氧化物对黏土进行了包覆改性,采用静态吸附法对该改性黏土吸附Cr(Ⅵ)的特性进行了研究,并考虑了反应时间、pH、浓度、温度对吸附的影响。实验结果表明,整个吸附过程基本在3h内完成;改性黏土对Cr(Ⅵ)的吸附量随溶液初始pH的增大而明显减小;随着溶液初始浓度和温度的增大而增大。同时,在初始pH为3.0的条件下,研究了改性黏土吸附Cr(Ⅵ)的动力学和热力学特性,结果表明,改性黏土对Cr(Ⅵ)吸附能较好地符合准二级动力学方程和Langmuir等温式。由Langmuir等温式得出,在293K、初始pH为3.0条件下的单层饱和吸附量为12.91 mg•g-1。确定了改性黏土吸附Cr(Ⅵ)的热力学参数,表明该吸附过程是一个吸热的自发过程。与原土的对比实验表明,改性黏土对Cr(Ⅵ)的吸附能力大大增强。     

Effect of chromium on accumulation and antioxidants in Cucumis utillissimus L.: Response under enhanced bioavailability condition

This study compares the accumulation of Cr(VI) and biochemical changes (total chlorophyll, carotenoid, protein, malondialdehyde (MDA) and cysteine contents) and roles of antioxidant enzymes (superoxide dismutase (SOD), guaiacol peroxidase (GPX), ascorbate peroxidase (APX)) in tolerance to metal induced stress in Cucumis utillissimus L. grown in Cr contaminated soil (CS) with garden soil (GS). Furthermore, Cr bioavailability was enhanced by ethylene diamine tetra-acetic acid (EDTA) addition to the soil to forecast the plant’s accumulation pattern at elevated Cr environment. Accumulation of Cr in the leaves of the plant increased with increase in substrate metals concentration. It further increased with the addition of EDTA by 1437% and 487% in GS and CS, respectively at the highest treatment level. The lipid peroxidation increased proportionately with increase in Cr accumulation in the leaves. All the activity of antioxidant enzymes (SOD, GPX and APX) and the level of cysteine increased with dose dependant manner. SOD and cysteine were observed to be higher in the GS than in CS, but APX and GPX were found to be higher in CS than in GS. The increase in GPX and APX activities with the increase in Cr concentration could be assumed that these two enzymes have a major role in the defense mechanism towards stress induced by Cr in C. utillissimus.     

响应面法优化复合微生物吸附剂对低浓度Cr3+的吸附

根据已有4种微生物吸附剂的吸附基团存在的差异特征,将其复配成复合吸附剂,借助统计学方法研究其对低ρ(Cr3+)废水的吸附性能.在单因素试验基础上,利用P-B(Plackett-Burman)法筛选出吸附过程4个主要影响因素分别为pH,初始ρ(Cr3+)及微生物吸附剂XB和TQ的投加量,应用最陡爬坡试验接近主要因素最优水平,采用Box-Behnken试验设计和响应面分析得到对低浓度Cr3+吸附过程的二阶模型.结果表明,最优吸附条件为pH 4.0,初始ρ(Cr3+)为4.86mg/L,XB和TQ的投加量分别为0.20和0.13 g/L,实际吸附率达到87.54%,与理论预测值(87.68%)接近,且高出单一吸附剂吸附率7.79%～17.35%.FT-IR扫描显示,复合微生物吸附剂性能提高与表面基团增多有关.通过响应面分析法优化复合微生物吸附,吸附性能明显提高.