化学沉淀组合电催化氧化处理脱硫废液技术研究

真空碳酸钾脱硫工艺碱洗段废液因含有高浓度硫化物、COD等有毒成分而影响焦化废水后续生物处理。以焦化企业实际碱洗段废液为研究对象,选用化学沉淀和电催化氧化的组合方式对其进行预处理。结果表明,室温下当氧化铜的投加量为65 g/L、反应时间60 min时废液中S2-去除率可达93%,且经过高温灼烧可实现Cu O沉淀剂的再生使用。沉淀后出水经电催化氧化处理,在电流10 A、电压4.9 V、电解时间120 min的条件下,出水COD可降至2 400 mg/L,满足常规生化系统进水的要求。     

有机过氧化物在生产、储运过程中的危险与可操作性分析

有机过氧化物的易燃、受热分解等特殊性质和生产、储运过程要求严格的低温条件与操作程序,使得有机过氧化物潜在的危险性很高。通过基于有机过氧化物危险特性及其在生产、储运过程中物质、能量与信息的分析,依据物-能量-信息的安全要素体系,应用危险与可操作分析方法,研究了有机过氧化物的安全理论,在某种程度上是延伸了HAZOP分析的内容。     

2014年春节期间北京市空气质量分析

对2014年1月30日(除夕)13时到1月31日(初一)12时期间北京市官园、怀柔和良乡监测站的CO、SO2、NOx、PM10、PM2.5浓度及PM2.5化学组分和能见度等监测数据进行分析,探讨了污染源减排和烟花爆竹燃放对北京市空气质量的叠加影响.研究发现,烟花爆竹的集中燃放会在短时间内造成严重的大气污染,其中,对PM10、PM2.5和SO2的影响最为显著.官园、怀柔和良乡监测站在1月31日凌晨1时的PM10浓度值分别为377.8、253.2和627.0μg·m-3,分别为1、2月份平均值的2.4、2.0和3.6倍;PM2.5浓度值分别为292.0、184.7和522.4μg·m-3,分别为1、2月份平均值的2.1、1.5和3.2倍.烟花爆竹的燃放对PM2.5化学组分中的K+、SO2-4、Cl-、Mg2+和Na+等影响最大,1月31日凌晨1时这5种离子在PM2.5浓度中占的比例高达92.1%.烟花爆竹的燃放造成1月31日凌晨1时监测中心和良乡的能见度分别降至2422 m和3591 m,是1、2月份能见度均值的22.9%和32.8%.2010—2014年"春节半月"期间官园、怀柔和良乡PM10平均浓度大多低于冬季均值和年均值,2014年"春节半月"这3个监测站的PM2.5浓度相比于冬季均值分别下降了33.3%、20.6%和39.2%,表明污染源减排对空气质量的正影响非常明显.     

广东某铀废石堆周边土壤中铀污染特征及其环境有效性

铀（U）矿冶过程中产生了大量铀废石。通常认为其放射性核素含量低,大多沿山谷露天自然堆放,一般不对堆场做防渗漏处置,对铀废石可能产生的潜在环境影响尚未引起重视。以广东某花岗岩型铀矿山的一个废石堆周边土壤为研究对象,在废石堆上、下游方向分别采集了2条（即BP1和BP2,视作背景土壤,距离废石堆的距离分别为10和20 m）和3条土壤剖面（即WP1、WP2和WP3,视作潜在U污染土壤,距离废石堆的距离分别为50、100和180 m）。通过对剖面间U分布特征的对比,定量估算了受污染土壤中外源U的输入通量;结合逐级化学提取技术,分析了U在土壤剖面的赋存形态及其环境有效性。结果表明：1）铀废石堆对周边土壤产生了显著的放射性污染,废石堆下游方向由近及远的3条U污染剖面（WP1、WP2和WP3）中U平均质量分数比背景剖面分别富集了634.6、10和3.7倍,其外源U的平均输入通量分别为4840.36、86.72和20.46μg·g-1。距污染源（废石堆）愈近,土壤中外源U的输入通量愈大;2）在近源区,大量的外源U优先在土壤表层聚集,随着远离污染源,逐渐转变为优先在剖面的深部淀积;3）与U 污染剖面相比,背景剖面（BP2）的惰性态 U（晶质铁锰氧化物/氢氧化物结合态+残渣态）所占比例最大,活性态 U（可交换态（包括水溶态）+碳酸盐结合态）所占比例最小,说明U污染土壤的外源U输入更倾向于对活性态U的贡献,这是对植物影响最直接的部分。另外,距污染源由近及远,U污染土壤中活性态U所占比例增大,潜在活性态U（有机质结合态+无定形铁锰氧化物/氢氧化物结合态）所占比例降低;4）3条U污染剖面中,平均90%以上的U（活性态和潜在活性态）对生态系统构成了威胁。因此,铀废石堆对周边环境产生的风险应得到充分重视。本研究为开展铀矿冶地域的放射性环境影响评价和土壤修复提供了有益的参考。     

磁微球负载硝基锌卟啉光催化剂的制备及催化性能研究

以氯化血红素为原料,制备了磁负载的硝基锌卟啉光催化剂.同时,利用热重分析仪(TG)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)和振动磁强计(VSM)对催化剂进行了表征,发现制备的催化剂负载率为32.06%,催化剂为粒径均一的球形壳-核结构,具有良好的磁性.其次,研究了催化剂的催化降解性能.结果表明,磁负载硝基锌卟啉光催化剂在可见光下,对水中的双酚A(BPA)、对硝基苯酚(PNP)等均有90%以上的去除率;对于活性红染料废水的降解也取得了83.67%的降解率.自由基捕获实验证明,电子(e-)、羟基自由基(·OH)、空穴(h+)和氧自由基(O-·2)是降解反应中重要的活性物种.最后通过GC-MS等手段对降解机理进行了研究.     

北京市PM_(2.5)主要化学组分浓度水平研究与特征分析

为研究北京市大气环境PM_(2.5)中主要化学组分特征,于2012年8月—2013年7月期间,在北京市定陵、车公庄、东四、石景山、通州、房山、亦庄和榆垡等8个点位开展为期1年的样品采集,共计采集472组样品,分析每组样品中OC、EC、水溶性离子和18种无机元素等组分.研究结果表明,本次研究的组分重建后和实际PM_(2.5)浓度相关性显著,相关系数为0.94,所测组分平均占PM_(2.5)总量的90%;各点位不同季节PM_(2.5)中主要的组分均为OC、NO_3~-、SO_4~(2-)、NH_4~+,呈南高北低的趋势,冬季OC是夏季的1.7倍,NO_3~-和SO2--4在四季呈交替状态,除榆垡点位的SO_4~(2-)NO_3~-外,其他点位均是NO_3~-SO_4~(2-),4种主要的组分质量浓度分别为(23.1±21.4)、(20.3±23.4)、(19.4±22.2)、(13.6±15.2)μg·m-3,占PM_(2.5)总含量的18.5%、16.3%、15.6%、10.9%;研究水溶性离子发现,8个点位全年SNA/PM_(2.5)比例为42.8%,其中,夏季最高(49.9%),秋季较低(31.1%),NO_3~-/SO_4~(2-)比值平均为1.05,相对往年研究结果 NO_3~-/SO_4~(2-)比值有增加的趋势.     

Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (·OH) and singlet oxygen (¹O₂) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of UOH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and ¹O₂. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.     

Growth and alkaline phosphatase activity of Chattonella marina and Heterosigma akashiwo in response to phosphorus limitation

The growth and alkaline phosphatase activity (APA) of two raphidophyceae species Chattonella marina and Heterosigma akashiwo were investigated in response to P-limitation and subsequent addition of dissolved inorganic phosphorus (DIP, NaH₂PO₄) and two dissolved organic phosphorus (DOP) compounds: guanosine 5-monophosphate (GMP) and triethyl phosphate (TEP). APAlevels increased greatly after P-starvation as the decrease of the cellular phosphorus quotes (Q_p). C. marina responded to P-limitation quickly and strongly, with 10-fold increase in APA within 24 hr after P-starvation. The larger difference between maximal and minimal Q_p values in C. marina indicated its high capacity in P storage. APA of H. akashiwo wasmaximally enlarged about 2.5 times at 48 hr of P-starvation. After the addition of nutrients, cell numbers of C. marina increased in all treatments including the P-free culture, demonstrating the higher endurance of C. marina to P-limitation. However, those of H. akashiwo increased only in DIP and GMP cultures. APA increased only after the addition of the monophosphate ester GMP. The results suggest that quick responses of C. marina to P-limitation, high capacity in P storage as well as endurance for P-depletion provide this species an ecological advantage in phytoplankton community competition under DIP-limited conditions.     

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

Biogenic volatile organic compound analyses by PTR-TOF-MS: Calibration, humidity effect and reduced electric field dependency

Green leaf volatiles(GLVs) emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds(BVOCs). Proton transfer reaction time-of-flight mass spectrometry(PTR-TOF-MS) is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field,etc. In this study the influence of gas humidity and the effect of reduced field(E/N) were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to10 ncps/ppbv(normalized counts per second/parts per billion by volume). The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity(RH) at 21°C, with the exception of(E)-2-hexenol. Product ion branching ratios were also affected by humidity,with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field(E/N) on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.