放射示踪法研究O2存在时14CS2与OH的光化学反应

用放射示踪法研究~(14)CS_2和OH的光化学反应,指出氧对反应有促进作用,在反应体系中(~(14)CS_2-H_2O_2-C_3H_8-N_2-O_2)主要产物为O~(14)CS,~(14)CO及少量~(14)CO_2。O~(14)CS和~(14)CO有相似的动力学曲线,~(14)CO_2则是另一种情况。总反应速率常数随氧压增加而增大,在氧压为33330Pa时,~(14)CS_2消失的总速率常数可高达3.4×10~(-12)cm~3mol~(-1)S~(-1)。在实验中观察到~(14)CS_2能在室温下转变为~(14)CO_2的现象。讨论了光化学反应的历程。     

Role of interfacial electron transfer reactions on sulfamethoxazole degradation by reduced nontronite activating H2O2

It has been documented that organic contaminants can be degraded by hydroxyl radicals ( • OH) produced by the activation of H₂ O₂ by Fe(II)-bearing clay. However, the interfacial electron transfer reactions between structural Fe(II) and H 2 O 2 for • OH generation and its effects on contaminant remediation are unclear. In this study, we first investigated the relation between • OH generation sites and sulfamethoxazole (SMX) degradation by activating H₂O₂ using nontronite with different reduction extents. SMX (5.2–16.9 μmol/L) degradation first increased and then decreased with an increase in the reduction extent of nontronite from 22% to 62%, while the • OH production increased continually. Passivization treatment of edge sites and structural variation results revealed that interfacial electron transfer reactions between Fe(II) and H 2 O 2 occur at both the edge and basal plane. The enhancement on basal plane interfacial electron transfer reactions in a high reduction extent rNAu-2 leads to the enhancement on utilization efficiencies of structural Fe(II) and H 2 O 2 for • OH generation.However, the • OH produced at the basal planes is less efficient in oxidizing SMX than that of at edge sites. Oxidation of SMX could be sustainable in the H 2 O 2 /rNAu-2 system through chemically reduction. The results of this study show the importance role of • OH generation sites on antibiotic degradation and provide guidance and potential strategies for antibiotic degradation by Fe(II)-bearing clay minerals in H 2 O 2 -based treatments.     

Theoretical study on the formation mechanism of polychlorinated dibenzothiophenes/thianthrenes from 2-chlorothiophenol molecules

Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes(PCDT/TAs),sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans(PCDD/Fs), has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol(2-CTP) as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene(1-MCTA), 1,6-dichlorothianthrene(1,6-DCTA), 4,6-dichlorodibenzothiophene(4,6-DCDT)and 1,6-dichlorodibenzothiophene(1,6-DCDT). The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.     

超声、过硫酸钾协同去除水中诺氟沙星的效果

过硫酸钾活化可产生强氧化性硫酸根自由基(SO-4·),采用超声/过硫酸钾体系氧化降解诺氟沙星,考察了过硫酸钾浓度、诺氟沙星初始浓度、溶液初始p H值及自由基淬灭剂甲醇、叔丁醇对降解效果的影响.结果表明,超声/过硫酸钾体系能够显著降解和矿化诺氟沙星,与单独过硫酸钾、超声相比,超声/过硫酸钾对诺氟沙星的去除率分别提高了3.2和8.9倍,降解过程符合一级反应动力学.诺氟沙星的去除率随过硫酸钾浓度的增加趋于平缓.p H对诺氟沙星的降解影响较大,这是因为随p H的升高,体系中的氧化性物种由SO-4·转化为以SO-4·/HO·为主.TOC去除和大肠杆菌抗菌实验表明,反应180 min,超声/过硫酸钾能够实现49.12%的诺氟沙星矿化,且对大肠杆菌的抑菌圈直径由45 mm减小到14 mm(滤纸直径),完全去除其抗菌性.结果表明超声/过硫酸钾能够有效用于诺氟沙星废水处理.     

Activated carbon enhanced ozonation of oxalate attributed to HO. oxidation in bulk solution and surface oxidation： Effect of activated carbon dosage and pH

Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol（tBA） with low dosages of AC,while it was hardly affected by tBA when the AC dosage was greater than 0.3 g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05 g/L, but it did not work when the AC dosage was no less than 0.1 g/L. These observations indicate that HOUin bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HOU oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5 g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HOUoxidation in basic bulk solution. A mechanism involving both HOUoxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.     

曝气加氢氧化钙复合技术抑制底泥磷释放及对底泥微生物多样性的影响

底泥磷释放是导致水体富营养化的主要原因之一,本文通过在样泥中分别投加0、0.01和0.02 mol·L-1Ca(OH)2溶液,同时进行微臭氧曝气(0.6 g·min-1),研究了曝气加氢氧化钙复合技术抑制底泥磷释放的效果及对底泥微生物多样性的影响.结果显示,投加0.02 mol·L-1Ca(OH)2组上覆水中总磷(TP)浓度的最终值与对照组相比,抑制率达到34%;从各形态磷的角度进一步分析发现,与对照组相比,该组底泥中可溶性磷和铁磷含量分别降低了92%和60%,其最终转化为钙磷是该技术的关键.通过聚合酶链式反应-变性梯度凝胶电泳技术(PCRDGGE)研究发现,各试验组微生物相似性在65%~85%之间;Berger-Parker优势度指数、Margalef丰富度指数、Shannon多样性指数变化不明显,表明该技术不会影响底泥微生物多样性.     

表面活性剂对以污泥为铝源制得的纳米Al（OH）3性质的影响研究

以污泥碳(SC)中回收的铝酸钠为铝源,在制备Al(OH)3的过程中加入表面活性剂PEG-1000(比例在0.01%~0.6%变化),考察其对Al(OH)3表面形貌和结构的影响.研究发现,当加入PEG-1000比例较小时,其空间位阻作用抑制了粒子之间的键合作用,使得Al(OH)3的沉淀效率较高、粒子尺寸较小,也能有效地阻止颗粒的团聚,SBET可以达到340 m2·g-1以上.当PEG-1000加入比例较大时,Al3+的沉淀效率逐渐降低,所得Al(OH)3粒子的尺寸变大,Al(OH)3的SBET和孔体积逐渐变小,平均孔径变大;原因是增多的PEG-1000分子会被包进Al(OH)3的结构中,限制了PEG-1000的表面交联和吸附,使空间位阻效应变差.—CH2—振动峰的出现说明PEG-1000是通过形成化学键的方式连接在Al(OH)3的表面基团上.PEG-1000的使用对于以污泥为铝源制备分散性好、尺寸较小和SBET较大的非晶态Al(OH)3具有重要作用.     

Herbicide Roundup® and its main constituents cause oxidative stress and inhibit acetylcholinesterase in liver of Carassius auratus

Roundup® is a glyphosate-based herbicide containing a mixture of surfactants. This paper evaluates the toxic effects of Roundup® and its main constituents on the goldfish, Carassius auratus, after 7 days exposure. Fish were exposed to 0.16, 0.032 and 0.0064 mg/L of Roundup® [containing 41% isopropylamine salt of glyphosate (G.I.S) and 18% polyoxyethylene amine (POEA)], G.I.S, and POEA. Their livers were taken for determining reactive oxygen species (ROS), superoxide dismutase (SOD) activity, malondialdehye (MDA) content and acetylcholinesterase (AChE) activity. Hydroxyl radical (·OH) could be induced by exposing Roundup® at a rate of 43%–111%, G.I.S at 90%–124% and POEA at142%–157%. A decreased SOD activity was observed in fish exposed to G.I.S and POEA. The contents of MDA significantly increased when exposed to Roundup® at all concentrations, 0.16 mg/L G.I.S and 0.032 mg/L POEA. The exposure led to an inhibition of AChE in livers overall during the experimental periods. POEA was more toxic than Roundup® or G.I.S during this experiment. AChE and ·OH are supposed to be sensitive biomarkers of the exposure of Roundup® and its main constituents to C. auratus.     

Effect of CuO on the efficiency of sulfur capture of Ca-based compounds during coal combustion

The efficiency of sulfur capture of CaO,Ca(OH)2 and CaCO3 as well as the effect of CuO on them were studied.Resulta showed that the efficiency of sulfur capture of Ca(OH)2 is the highest among these three compounds.When CuO was used with each of CaO,Ca(OH)2 and CaCO3 at the same time,the efficiency of all of them would rise,and that of Ca(OH)2 raise most.The efficiency of sulfur capture of Ca(OH)2 with CuO is 14.4% higher than that without CuO.     

二羟基苯甲酸的硅烷化及其在气质联用测量气相OH自由基的应用

通过优化GC-MS参数有效分离了水杨酸(SA)及其羟基化产物2,3-DHBA和2,5-DHBA的硅烷化产物,检测限分别为10.2 fmol和9.9 fmol.采用浸渍膜捕集OH标准源发生体系产生的OH自由基,测得气相OH自由基与固相SA反应生成的2,3-DHBA 和2,5-DHBA的产率分别为52%和48%.因此,SA捕集-硅烷化衍生-气质联用测量方法研究大气OH自由基有很好的应用前景.