Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Hunting Increases Dispersal Limitation in the Tree Carapa procera, a Nontimber Forest Product

Abstract:  The sustainability of seed extraction from natural populations has been questioned recently. Increased recruitment failure under intense seed harvesting suggests that seed extraction intensifies source limitation. Nevertheless, areas where more seeds are collected tend to also have more intense hunting of seed-dispersing animals. We studied whether such hunting, by limiting disperser activity, could cause quantitative dispersal limitation, especially for large crops and for crops in years of high seed abundance. In each of four Carapa procera (Meliaceae) populations in French Guiana and Surinam, two with hunting and two without, we compared seed fate for individual trees varying in crop size in years of high and low population-level seed abundance. Carapa seeds are a nontimber forest product and depend on dispersal by scatter-hoarding rodents for survival and seedling establishment. Hunting negatively affected the proportion of seeds dispersed and caused greater numbers of seeds to germinate or be infested by moths below parent trees, where they would likely die. Hunting of seed-dispersing animals disproportionally affected large seed crops, but we found no additional effect of population-level seed abundance on dispersal rates. Consistently lower rates of seed dispersal, especially for large seed crops, may translate to lower levels of seedling recruitment under hunting. Our results therefore suggest that the subsistence hunting that usually accompanies seed collection is at the cost of seed dispersal and may contribute to recruitment failure of these nontimber forest products. Seed extraction from natural populations may affect seedling recruitment less if accompanied by measures adequately incorporating and protecting seed dispersers.     

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.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

石灰对生物炭和腐殖酸阻控水稻Cd吸收的效应

采用田间试验,研究了石灰-生物炭和石灰-腐殖酸两种联合修复剂及其不同施用量对酸性土壤中稻米Cd含量、产量和品质的影响,并对不同处理修复效果进行综合评估.结果表明,两种联合修复剂能显著降低稻米Cd含量17.39%~45.96%,降低土壤有效Cd含量18.29%~29.88%,.生物炭、腐殖酸施用量分别为5000,6000kg/hm²时,稻米Cd的降低效果最佳.石灰-生物炭处理中,降低稻米Cd含量的主要因子为土壤pH和土壤有效Cd含量（P<0.05）,而石灰-腐殖酸处理则为土壤有机质含量与土壤有效Cd含量（P<0.05）.施加修复剂后稻米产量可达6637~7890kg/hm²,直链淀粉含量达到19.47%~27.26%;当腐殖酸施用量为7500kg/hm²时可使稻米产量提高10.97%,而石灰-生物炭处理对稻米产量无显著影响;采用层次分析法确定了稻米Cd含量、稻米产量、稻米品质和修复费用在修复效应评估中所占权重为0.608、0.150、0.102、0.140,综合评估结果显示土壤-水稻系统Cd阻控效应的联合修复技术为：在施用1200kg/hm²石灰的基础上同时施加6000kg/hm²腐殖酸.     

氧基氯化铁非均相活化过一硫酸盐降解金橙Ⅱ

采用部分热分解法制备了氧基氯化铁（FeOCl）,用于活化过一硫酸盐（PMS）降解难降解偶氮染料金橙Ⅱ（AO7）.利用X射线光电子能谱分析（XPS）、扫描电镜（SEM）和X射线衍射光谱（XRD）对其进行了表征;通过实验评估FeOCl/PMS体系对AO7的降解效果并分析了影响AO7去除率的各种因素.结果表明：FeOCl活化PMS降解AO7效果良好,矿化率达44%.在中性条件下,当FeOCl投加量50mg/L、PMS浓度1.0mmol/L、AO7浓度0.05mmol/L时,AO7可在30min内完全降解.随PMS投加量、FeOCl投加量、Cl^-浓度和反应初始pH值的增大,AO7的脱色效果提高.FeOCl还具有良好的重复利用性.此外,通过自由基淬灭实验、EPR测试和XPS分析了反应的主要活性物种和反应机理：由PMS活化产生的SO₄^-·和·OH对污染物进行降解,其中主要活性物种为SO₄^-·.     

联合改良剂对桉树吸收重金属的作用——以矿区土壤中Cd、Zn和Cu为例

通过5种矿区土壤的盆栽试验,研究了联合改良剂对桉树部分生理指标、根中Cd、Zn和Cu的含量、以及土壤中Cd、Zn和Cu的BCR提取形态的影响,探讨了其对矿区土壤还林的作用.结果表明,与对照相比,施用改良剂后桉树的生物量和叶绿素含量的增幅分别为-7.6%~158.8%和-0.7%~23.1%,丙二醛含量的降幅为2.6%~37.9%,其中部分处理的生物量和丙二醛含量的变化达到显著水平（P<0.05）;土壤中有效态Cd、Zn和Cu的含量分别下降12.5%~63.8%、1.6%~54.7%和16.2%~57.6%,桉树根中Cd、Zn和Cu的含量分别下降3.1%~56.6%、-1.5%~21.3%和9.3%~50.1%.土壤对桉树根中Cd、Zn和Cu的含量有显著影响（P<0.05）,改良剂的配比或施用量无显著影响（P>0.05）,但在5种矿区土壤中G3降低桉树根中Cu含量的效果优于G1和G2;在重金属含量最高的2种土壤中,G1降低桉树根中Cd和Zn含量的效果优于G2和G3.研究表明施用联合改良剂能降低桉树对重金属的吸收,有利于矿区土壤的还林.     

腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

铝合金的实验室盐雾试验腐蚀行为图像特征提取

目的提取铝合金材料在盐雾箱试验中可以表征腐蚀程度的表面形貌图像特征量。方法首先,对采集于表面化学清洗过的试样原始图像进行图像增强等预处理,突出腐蚀部位;其次,基于数字图像处理的分形和小波分解方法提取出分形维数和小波能量特征值。结果与以质量损失量为基础的腐蚀深度特征值进行相关性对比,基于图像分析的特征提取法的准确度和精度比较高。结论该方法可以应用于对试样的腐蚀程度进行定性和定量分析,判断并预测试样的腐蚀速度。