新型多金属氧酸盐K_7BiW_(11)O_(39)Sn·11H_2O制备及光催化降解模拟染料废水

本文采用水热合成法首次制备了一种新型多金属氧酸盐,采用扫描电镜(SEM)、扫描电镜-能谱(SEM-EDS)、X射线光电子能谱(XPS)、X射线衍射(XRD)、热重-差热分析(TG-DSC)、紫外可见吸收光谱(UV-Vis)、傅里叶变换红外光谱(FTIR),电感耦合等离子体发射光谱(ICP)等技术对其进行了表征,结果表明,所制备的化合物具有Keggin结构,为非晶体化合物,其分子式为K_7BiW_(11)O_(39)Sn·11H_2O(BiW_(11)Sn).以酸性红299(AR299)为目标降解污染物,研究了自然日光辐照下BiW_(11)Sn均相光催化AR299水溶液脱色降解活性.结果表明,BiW_(11)Sn能有效的光催化AR299脱色降解.AR299溶液的初使pH值、初始浓度、催化剂投加量、光解时间对AR299光催化降解效果均有影响.20 mL,4 mg·L~(-1),初始pH值为5.4的AR299水溶液(溶液中BiW_(11)Sn浓度为0.5 g·L~(-1)),阳光下辐照3 h,其脱色率达到93.1%;其光催化降解反应遵循LangmuirHinshelwood准一级动力学方程;超氧负离子自由基为光催化降解过程中的重要活性物种.     

混合菌株对三溴苯酚的降解特性

为提高有害物质2,4,6-三溴苯酚（TBP）的有效生物降解效果,在比较了不同菌株对TBP的降解状况的基础上,着重考察了诱变菌株TBPY UMP-f与粘质沙雷氏菌株SMA混合降解TBP的效果.结果表明,混合菌株比单一菌株降解效果好.考察影响混合降解相关因素的结果表明,适宜条件为两菌接种比例1∶1,SMA适于在TBPY U...     

固定化微生物对土壤中苯并芘的降解

研究了3株细菌与3株真菌对土壤中苯并芘（BaP）的降解动态,从中筛选出1株细菌（Bacillus sp.）和1株真菌（Mucor sp.）,并采用吸附法将混合菌固定在改性后蛭石上,研究了固定化混合菌对土壤中BaP的降解效果。结果表明：细菌中芽孢杆菌（Bacillus sp.,SB02）降解率最高,42 d对B[a]P的降解率为33.0%,降解速率也最快,1周可降解12.6%的BaP;真菌中毛霉（Mucor sp.,SF06）降解率最高,42 d对B[a]P的降解率为69.7%;以改性后蛭石为载体用吸附法制得的固定化混合菌,传质性能好,对BaP的降解率42 d可达95.32%,高于游离菌20个百分点。     

辛基酚聚氧乙烯醚好氧生物降解产物的GC-MS测定

从上海闵行区污水处理厂曝气池中的污泥和上海孙桥农业园区农田表层土壤样品中分离得到两株好氧降解菌株：B16-2（曝气池）和N1（农田）,都能够不同程度地降解辛基酚聚氧乙烯醚（OPEOn）.利用气相色谱-质谱联用仪对其好氧生物降解产物进行了表征和鉴别.结果表明,两株菌对OPEOn的好氧生物降解都产生了环境雌激素活性物质--辛基酚,从曝气池中分离出的B16-2好氧降解产生了丁基酚聚氧乙烯醚,从仙人掌土壤分离出的N1菌株降解以羟基端EO链的逐渐断裂为主要途径.     

电镀厂污染土壤重金属形态及淋洗去除效果

以某电镀厂污染场地重污染区域土壤为研究对象,对土壤中重金属全量和各形态含量进行分析,并研究筛选高效土壤淋洗剂,比较其淋洗去除效果。结果表明,该土壤以铬和镍污染最为严重,土壤铬和镍含量分别达1 564.00和679.00 mg.kg-1,土壤铜、锌和铅含量分别为297.00、276.00和51.40 mg.kg-1,铜、铬、镍、锌和铅的有效态比例分别为41.77%、13.16%、28.08%、21.50%和31.18%。去离子水、盐酸、乙酸、草酸、柠檬酸和EDTA 6种淋洗剂中,去离子水对5种重金属提取量均较少;草酸对铜、铬、镍和锌去除效果较好,去除率分别为55.1%、24.8%、47.5%和29.3%;柠檬酸对铜、铬、镍和锌去除效果较好,去除率分别为26.3%、25.7%、33.0%和21.6%;EDTA对铜、镍、锌和铅去除效果较好,去除率分别为31.5%、28.9%、21.4%和30.6%。综合考虑淋洗剂的提取效果、水溶性以及操作难度和成本,建议采用柠檬酸作为淋洗剂,最佳液土比〔V（液）∶m（土）〕为10∶1,最佳淋洗时间为6 h。     

土壤环境中具有Keggin结构的Al13草酸盐胶体合成及其表征

采用XRD,FTIR和MAS27 Al NMR方法表征从Al13溶液中合成的草酸盐胶体.结果表明:胶体具有明显的XRD衍射峰,有别于常见的Al系及其草酸盐沉淀;位于810cm-1处络合物中Al-O伸缩振动证明胶体是由Al13和草酸根直接络合形成;红外光谱中位于725cm-1处的(Al-O)Td键和固体核磁共振波谱中位于约61ppm处的Al(O)4特征峰共同证明胶体具有特殊的Keggin结构,高pH(=7.8)环境下Al13草酸盐胶体仍能保持Keggin结构;经过化学分析,该草酸盐胶体化学式为AlO4Al12(OH)24(H2O)12(C2O4)7/2.     

联合多种荧光光谱和GC-MS研究高铁酸钾对菲的降解机理

研究了高铁酸钾对PAHs中的菲的降解反应过程,对该反应过程联合了时间扫描、偏振、偏振三维(PEEM)、三维(EEM)等多种荧光光谱模式进行了表征和分析,并结合GC-MS进一步检测分析了该反应过程的中间产物,最后系统探讨了高铁酸钾对菲降解的动力学反应规律及降解机理.实验结果表明,在设定的高铁酸钾-菲降解体系的物质的量之比为1∶1、1∶2、1∶3、2∶1、3∶1的各个降解反应过程均符合一级反应动力学特征,其拟合系数在0.905—0.995之间.通过不同摩尔比的高铁酸钾-菲降解过程的时间扫描荧光参数直接求得了各反应的动力学方程及曲线;菲降解过程的荧光偏振度值与PEEM共同揭示出高铁酸钾对菲的有效降解,且产物均为无偏振效应、无产生新的特征荧光的小分子结构,各特征光谱峰强与时间变化关系也与时间扫描荧光曲线相符合;最后结合GC-MS深入分析了菲的降解产物,并由此推测了高铁酸钾对菲的降解机理.降解产物中9,10-菲醌的大量存在表明菲结构中9,10位发生氧化而开始降解.     

ZrO2掺杂的V2O5/TiO2催化剂表征及催化还原NOx

采用共沉淀法制备出不同锆掺杂量的钛锆复合载体(TiO2-ZrO2),运用XRD和BET研究其微观结构,结果显示钛锆物质的量之比1∶1时复合载体具有最大的比表面积,可达256.01 m.2g-1.以此为载体制备了V2O5/TiO2-ZrO2催化剂,并添加少量CeO2对其改性.采用XRD、BET、H2-TPR、原位FT-IR等手段研究其活性组分的表面分散状态、氧化还原特性和表面酸性.结果显示,V2O5高度分散在载体上;与纯V2O5相比,复合载体上V2O5的还原峰向低温方向发生了偏移;催化剂表面包含了大量的B酸和L酸.模拟氨气催化还原NO(NH3-SCR)的脱硝反应活性测试表明,V2O5/TiO2-ZrO2催化剂具有较好的热稳定性和较宽的活性窗口,少量CeO2的加入提高了催化剂的低温活性.     

甲氧苄啶在有机酸络合Fe~(2+)活化过硫酸钠体系中的降解机制

在有机酸(OAS)/Fe~(2+)/过硫酸钠(PDS)体系中生成的具有强氧化能力的硫酸根自由基(SO_4~(·-)),可以降解水中难降解污染物甲氧苄啶(TMP).分别探讨了柠檬酸(CA)浓度、Fe~(2+)浓度、PDS浓度、p H值对甲氧苄啶降解的影响,以及不同浓度的4种有机酸在不同p H值下对TMP降解的影响.结果表明,当TMP浓度20μmol·L~(-1),p H=7,温度25℃,反应时间30 min,摩尔比CA∶Fe~(2+)∶PDS∶TMP=5∶15∶40∶1时,TMP的降解率高达82.55%;柠檬酸和EDTA有促进TMP降解作用,焦磷酸钠和草酸起抑制TMP降解作用.猝灭实验证实了TMP的降解是SO_4~(·-)和·OH共同作用的结果,SO_4~(-·)起主导作用;液相色谱质谱检出5种中间产物,推测TMP的降解路径涉及羟基化反应、脱甲氧基化反应和裂解反应.     

基于木质素生物降解的堆肥化接种剂开发

选取由农林废物堆肥中筛选出的木质素降解优势土著微生物枯草芽孢杆菌(Bacillus subtilis)、铜绿假单孢菌(Pseudomonas aeruginosa)、黑曲霉(Aspergillus niger)、简青霉(Penicillium simplicissim)、栗褐链霉菌(Streptomyces badius),依据PLFA-PLS定量分析所得堆肥化2次发酵期有效的木质素降解微生物群落组成比例混合接种至稻草基质发酵瓶中,做1组L9(34)正交试验以优化混合比例,期望开发1种基于木质素降解的高效堆肥化接种剂.试验结果表明:混合菌剂具有较强的木质素降解能力,其对木质素的降解是木质素过氧化物酶、锰过氧化物酶、漆酶、纤维素酶和半纤维素酶共同作用的结果;当按照个数比细菌∶放线菌∶真菌为85∶5∶ 10,枯草芽孢杆菌∶铜绿假单孢菌为55∶25,黑曲霉∶简青霉为2∶1配比时,木质素、纤维素、半纤维素降解率最高,分别达到22.13%,48.97%和55.93%;在不灭菌前提下,按此配比接入菌剂,其木质素、纤维素、半纤维素降解率分别比不接菌剂发酵稻草提高19.16,38.25和46.30百分点.     

焙烧态镁铝铁类水滑石对磷酸根离子的吸附

用共沉淀法制备了镁铝铁三元类水滑石(LDH),在不同温度下对其焙烧4 h,得到焙烧态类水滑石(CLDH).采用XRD、FT-IR对材料进行分析,研究其对水中磷酸根的吸附性能和机制.结果表明,铁的掺杂量过大会破坏类水滑石的层状结构,且随着铁含量的增大,类水滑石对磷酸根的吸附量逐渐减小.当Mg/Al/Fe物质的量之比为2∶0.9∶0.1,在300℃下焙烧时,CLDH吸附磷酸根能力最好,吸附容量约27.03 mg.g-1,为焙烧前的1.32倍.在pH 4—11范围内,在竞争离子存在的条件下,CLDH-0.1-300都能表现出较好的吸附性能,对实际废水中的磷也有较强的吸附能力.CLDH-0.1-300对磷酸根的吸附符合二级反应动力学模型,吸附等温线符合Langmuir等温式.用浓度为0.5 mol.L-1的NaOH溶液可以对吸附磷酸根后的类水滑石CLDH-0.1-300实现解吸再生,"吸附-再生-再吸附"循环3次后吸附容量仍接近初始值的60%.     

NiFe2O4直接分解二氧化碳成碳循环反应过程结构演变研究

用XRD Rietveld分析法,对共沉淀法制备的NiFe2O4在H2／CO2循环反应中的结构演变进行研究,发现随着循环反应次数的增加,NiFe2O4物相的含量逐渐降低,Fe2Ni1-x物相的含量及其(200)衍射的平均晶粒逐渐增大,并出现Fe3C物相,其含量增长较快．纯NiEe2O4经15次循环反应后,体系中NiFe2O4物相的含量只剩下5％左右,样品基本失去分解CO2的活性．NiFe2O4掺杂4％铬后,明显提高了NiFe2O4骨架结构的稳定性,虽经50次H2／CO2循环反应,体系中NiFe2O4物相含量仍然有20％,分解CO2的活性仍达到初始活性的40％．     

哈尔滨市降雪中溶解性有机物光谱特性分析

研究雨雪中的溶解性有机物(DOM)将有利于把握其理化性质及其在生态系统中的行为和功能.本研究运用三维荧光光谱(EEMs)技术结合平行因子分析(PARAFAC)、紫外-可见光谱技术(UV-vis),对哈尔滨市2018年3月1日降雪样品中DOM的光谱特性及来源进行解析.结果表明,降雪样品中DOM的相对分子质量较大,芳香构造程度较高,C=C不饱和双键结构较多,腐殖化程度更高,结构更复杂,芳环上含氧官能团含量较少,有机质疏水性较强;EEMs结合PRAFAC解析出3种组分,分别为类腐殖质类物质(C₁和C₂)和类色氨酸(C₃),荧光特征参数(荧光指数FI、自生源指数BIX、腐殖化系数HIX_b和新鲜指数β∶α)表明,降雪样品中DOM受陆源和生物源同时作用,腐殖化程度较高且受到陆源影响严重,自生源组分较少,新生成的DOM比例较低.     

Concentrations and modes of occurrence of trace elements in the Late Permian coals from the Puan Coalfield, southwestern Guizhou, China

The concentration, mode of occurrence, and origin of trace elements in the Late Permian coals from the Puan Coalfield, southwestern Guizhou, China, were examined using inductively coupled plasma-mass spectrometry (ICP-MS), X-ray fluorescence (XRF), cold-vapor atomic absorption spectrometry (CV-AAS), ion-selective electrode method (ISE), sequential chemical extraction procedure (SCEP), scanning electron microscopy equipped with energy-dispersive X-ray (SEM-EDX), and optical microscope. Results show that minerals in the No. 2 Coal from the Puan Coalfield were mainly made up of epigenetic pyrite of low-temperature hydrothermal fluid origin and kaolinite of detrital terrigenous origin. Elements including As (36.9 μg/g), Cd (10.2 μg/g), Cr (167.3 μg/g), Cu (365.4 μg/g), Hg (2.82 μg/g), Mo (92.6 μg/g), Ni (82.6 μg/g), Pb (184.6 μg/g), Se (6.23 μg/g), Zn (242.3 μg/g), and U (132.7 μg/g) are significantly enriched in the No. 2 Coal from the Puan Coalfield. However, concentrations of trace elements in the other four coals, the No. 1, No. 8, No. 11, and No. 18 Coals, were close to the usual ranges found for Guizhou of China, China, and USA. Results of SEM-EDX and SCEP showed that As, Cd, Hg, Mo, Ni, Pb, and Zn occur mainly in veined pyrite, while Cr, Cu, and U distribute mainly in kaolinite, indicating that the low-temperature hydrothermal fluid and detrital materials of terrigenous origin are the main contributors to the enrichment of these trace elements in the No. 2 Coal.     

The Impact of the Hyperacid Ijen Crater Lake. Part I: Concentrations of Elements in Crops and Soil

In Asembagus (East Java, Indonesia) irrigation water is contaminated with effluent from the hyperacid Ijen Crater Lake resulting in a low pH and high levels of various elements. As a first step towards a risk assessment, locally produced food items (rice, maize, cassava leaf, cassava root, peanuts) were collected and concentrations of As, B, Ca, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Pb, V, Zn were compared to samples from a reference area and with literature values. Further, concentrations in rice were compared to total soil concentrations in paddy fields. Compared to the reference area, food items produced in the contaminated area had increased levels of Cd, Co, Ni and Mn in particular, while levels of Mo were lower. In contrast, total soil concentrations of Cd and Mn in particular have decreased whereas especially Mo was increased. In combination with the observed soil acidification, it is likely that the bioavailable concentration of most elements in the contaminated soil is higher (except for Mo) due to an increased weathering rate and/or input via the contaminated irrigation water. In terms of human health, concentrations in foods were generally within normal literature values. However, it was observed that essential elements (in particular Fe) known for their inhibitory effects on e.g. Cd and Mn toxicity did not accumulate in crops whereas Cd and Mn did.     

大气PM2.5中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1(可溶态与可交换态)和F2(碳酸盐态、可氧化态与可还原态),绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3(有机质、氧化物与硫化物结合态),Cu主要以F2和F3存在,Cr主要分布在F3和F4(残渣态),Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态(F1)比例比2006年秋普遍增加,次稳定态(F2、F3)比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高(>0.7),属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

不同使用年限蔬菜大棚土壤重金属含量变化

调查了 1、5、8、1 1a棚龄蔬菜大棚土壤中重金属元素As、Cd、Co、Cr、Cu、Hg、Fe、Mn、Mo、Ni、Pb和Zn的含量。结果表明 :同一使用年限的蔬菜大棚 0～ 40cm土层内重金属元素含量差异很小 ;与棚外土壤相比 ,除 1a棚龄的土壤外 ,多数土壤重金属含量随大棚使用年限的延长而有所增加 ;研究地区的蔬菜大棚土壤尚未发生重金属污染超标现象 ;大量施肥 (复合肥 )可能是导致蔬菜大棚土壤中重金属含量升高的主要原因     

Relationships between distributions of longevous population and trace elements in the agricultural ecosystem of Rugao County,Jiangsu, China

Soil, plant, and water, as well as trace elements they contain, can influence human health through the food chain. A survey was conducted on distributions of trace elements in soils, plants, and drinking water in Rugao County, Jiangsu Province, China, an agricultural area with a high level of centenarians and nonagenarians. The ratio of people over 90 years old per 100,000 inhabitants (90-rate) based on village (about 4,000 residents in 4 km²) was correlated with trace elements in soil, drinking water, and rice by means of correlation analysis and/or principal component analysis. Although the average 90-rate in the whole area was as high as 277, the rates were not uniform across the entire region. The 90-rate in the area of loamy and strongly-developed Anthrosols and Cambosols was about 330, significantly higher than the 255 in the areas of sandy and strongly-developed Cambosols and of clayey and weakly-developed Cambosols. The concentrations of available Se, B, Ni, and Mo in soils of the area with the high 90-rate were markedly greater than those in the area with the low 90-rate. This was demonstrated by highly positive correlations between the 90-rate and available Se (r = 0.33), B (r = 0.21), Ni (r = 0.17) and Mo (r = 0.17) at the p < 0.01 level and high loadings of available Se (0.851), B (0.535), Ni (0.594) and Mo (0.394) in the longevous factor. Similar relationships between the available elements in soils and elements in water and rice were found. These results suggest that: (1) the available forms of elements in soil were more crucial to elemental bio-availability in the ecosystem and human health than total elements in soil; and (2) the element association above might have affected the 90-rate positively and could be an important environmental geochemical factor influencing the longevity of humans.     

厌氧好氧一体化生物反应器处理发酵废水的研究

采用新型厌氧好氧一体化生物反应器对发酵废水进行了中试处理研究.试验结果表明,系统总有机负荷最高可达到8.88kg(COD)m-3d-1,系统去除率稳定在88.10%~96.88%,说明反应器处理效率高,抗冲击能力强.反应器结构合理,利于保持丰富、高活性的微生物,反应器厌氧区颗粒污泥TS高达83.9gL-1,VS/TS为56.9%~57.4%,比产甲烷活性为280~350mL(CH4)gvss-1d-1;好氧区固定化微生物TS高达64.03gL-1载体,VS/TS为94.02%~94.30%.反应器各功能区对废水的降解过程分析,说明反应器厌氧区和好氧区一体化结构合理,可将废水逐级降解,从而保证整个系统的处理效果.图8表4参11