Competing pathways of cresol formation in toluene photooxidation: OH-toluene adducts react with NO2 or with O2?

Methyl-hydroxy-cyclohexadienyl radicals (OTAs) are the key products of the photooxidation of toluene, with implications for the fate of toluene. Hence, we investigated the photooxidation mechanisms and kinetics of three main OTAs (o-OTA, m-OTA, and p-OTA) with NO₂ using quantum chemical calculations as well as the fate of OTAs under the different concentration ratios of NO₂ and O₂. The mechanism results show that the pathway of H-abstraction by NO₂ to anti-HONO (anti-H-abstraction) is more favorable than the syn-H-abstraction pathway, because the strong interaction between OTAs and NO₂ is formed in the transition states of the anti-H-abstraction pathways. The branching ratios of the anti-H-abstraction pathways are more than 99% in the temperature range of 216−298 K. The total rate constant of the OTA-NO₂ reaction is 9.9 × 10⁻¹² cm³/(molecule∙sec) at 298 K, which is contributed about 90% by o-OTA + NO₂, and the main products are o-cresol and anti-HONO. The half-lives of the OTA-NO₂ reaction in some polluted areas of China are 35 times longer than those of the OTA-O₂ reaction. In the atmosphere, the NO₂- and O₂- initiated reactions of OTAs have the same ability to form cresols as [NO₂] is up to 142.1 ppmV, which is impossible to achieve. It implies that under the experimental condition, the [NO₂]/[O₂] should be controlled to be less than 7.8 × 10⁻⁵ to simulate real atmospheric oxidation of toluene. Our results reveal that for the photooxidation of toluene, the yield of cresol is not affected by the concentration of NO₂ under the atmospheric environment.     

坡耕地不同作物及有无树篱对土壤微生物群落结构与多样性的影响研究

为研究种植不同作物及有无树篱的坡耕地中土壤微生物群落结构与多样性是否有差异,以湖北秭归张家冲水土保持站试验田坡耕地有无树篱及3种典型作物(茶树、柑橘、花生)搭配共计6种样地为研究对象,测定其土壤的理化性质,并通过16S rDNA测序法对土壤微生物群落组成与多样性进行研究。结果表明:不同作物及有无树篱均对土壤微生物群落组成与多样性有显著影响(p0.05);花生样地含有最多种类的土壤微生物(p0.05),其土壤微生物多样性最高;无树篱样地土壤微生物门和目的数目高于有树篱样地;研究样地中土壤微生物优势种类在门的水平上有变形菌门(Proteobacteria)占总数的23.22%、酸杆菌门(Acidobacteria)16.59%、浮霉菌门(Planctomycetes)14.81%、放线菌门(Actinobacteria)9.38%,在属的水平上有DA101属11.34%、慢生根瘤菌属(Bradyrhizobium)8.77%、出芽菌属(Gemmata)6.19%、红游动菌属(Rhodoplanes)5.05%;土壤微生物分布受土壤理化性质的影响,酸杆菌门和变形菌门细菌丰度与土壤pH值呈显著正相关(p=0.042),说明土壤pH值显著影响土壤微生物的分布。     

纳氏试剂比色法测定污水中氨氮的优化研究

纳氏试剂比色法测定污水中氨氮,其蒸馏预处理过程存在耗时长、馏出液接收不便和操作繁琐等问题.文章对预处理及测定方法进行了优化,提出将水样蒸馏体积减少为50 mL,后期比色体积减少为25 mL,并去除硼酸吸收液,改为直接接收馏出液.经验证,其结果与国标方法无显著性差异,标样验证相对误差为-0.8%~0.9%,实际样品测定结果的相对标准偏差为0.9%~4.4%,加标回收率为94%~107%.优化的方法测量数据稳定,结果准确,在测定污水中氨氮具有实际应用意义.     

青岛沿海地区一次臭氧重污染过程的特征及成因分析

近年来,青岛市夏季臭氧(O_3)污染逐渐严重,深入分析青岛的O_3变化特征和重污染形成机理对该地区大气污染防治具有重要意义.本文基于青岛大气监测站2017年6月1—20日的O_3小时浓度数据,分析了发生在青岛沿海地区的一次持续O_3重污染过程的特征,并利用数值模式进行成因分析.结果表明,本次污染过程10个监测站日最大8 h平均臭氧浓度超标率达到30%～45%,超标倍数为0.20～0.51,单站小时浓度峰值可达390μg·m~(-3).同时,利用WRF-CMAQ模型对O_3重污染过程进行了数值模拟、过程分析和敏感性试验.结果表明,WRF-CMAQ具有模拟臭氧重污染的能力,6月8—9日、15—16日O_3重污染主要是外部输送导致,可能的机制是上游高空的高浓度O_3沿气团轨迹传输,随下沉气流聚集在青岛西南部海面,随后由近地层西南向海风水平输送至青岛沿岸,而6月17日O_3重污染产生的首要因素是局地光化学生成.本次臭氧污染期间,青岛大部分时间都处于前体物非敏感区,且覆盖范围广.2017年6月1—20日青岛沿海地区的臭氧污染事件大部分归因于区域传输,因此,应该加强区域联防联控,减少区域传输对城市臭氧浓度的影响.     

寨上金矿矿区河流沉积物中砷的形态分析

在野外调查和样品采集的基础上,对寨上金矿矿区河流沉积物中砷的质量分数进行了测定,并采用Tessier连续提取法对砷在沉积物中的存在形态进行了提取分析。结果表明,砷在该区水系沉积物中质量分数较高（55.0~189.0μg.g-1）,说明金矿的开采已经对该区的环境造成了影响。运用Tessier连续提取法研究发现,沉积物样品中砷的提取率为89.87%~110.54%,样品沉积物中砷的形态分布基本一致,以残渣态为主,占其总量的85%以上,其他各形态相对含量较少,但相对活泼形态（水溶态、离子交换态和碳酸盐结合态）绝对质量分数较高（2.029~4.942μg.g-1）,说明该区水系沉积物中大部分砷在自然条件下相对比较稳定,小部分砷（1.10%~5.55%）易释放至环境中,但由于其绝对质量分数较高,将对环境产生较大危害。     

磷酸铵镁沉淀法脱除生活污水中氮磷的研究

针对低有机物高氨氮浓度的生活污水,经UASB处理后的厌氧废水,氮含量较高,磷基本未除去,处理出水效果欠佳的情况,提出磷酸铵铗沉淀法脱除生活污水中的磷以及部分氨氮。初步确定了影响磷酸铵镁沉淀反应因素为pH值,Mg^2＋：PO4^3-：NH4^＋,反应时间t。最优反应条件为：pH=8．5,Mg^2＋：PO4^3-：NH4^＋=1．2：1：1,反应时间t=1min。磷的去除率可高达94．0％,氨氮的去除率达71．5％,为低浓度的生活污水的后续生物处理创造了良好的条件。     

An E. coli SOS-EGFP biosensor for fast and sensitive detection of DNA damaging agents

An E. coli SOS-EGFP biosensor which expresses enhanced green fluorescent protein as a reporter protein under the control of recA gene promoter in SOS response was constructed for detection of DNA damage and evaluation of DNA damaging chemicals. The chemicals that may cause substantial DNA damage will trigger SOS response in the constructed bacterial biosensor, and then the reporter egfp gene under the control of recA promoter is stimulated to express as a fluorescent protein, allowing fast and sensitive fluorescence detection. Interestingly, this biosensor can be simultaneously applied for evaluation of genotoxicity and cytotoxicity. The SOS-EGFP bacterial biosensor provides a sensitive, specific and simple method for detecting known and potential DNA damaging chemicals.     

Combined remediation of DDT congeners and cadmium in soil by Sphingobacterium sp. D-6 and Sedum alfredii Hance

Combined pollution of 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (DDT) and cadmium (Cd) in agricultural soils is of great concern because they present serious risk to food security and human health.In order to develop a cost-effective and safe method for the removal of DDTs and Cd in soil,combined remediation of DDTs and Cd in soil by Sphingobacterium sp.D-6 and the hyperaccumulator,Sedum alfredii Hance was investigated.After treatment for 210 days,the degradation half-lives of DDTs in soils treated by strain D-6 decreased by 8.1% to 68.0% compared with those in the controls.The inoculation of strain D-6 into soil decreased the uptake of DDTs by pak choi and S.alfredii.The shoots/roots ratios of S.alfredii for the Cd accumulation ranged from 12.32 to 21.75.The Cd concentration in soil decreased to 65.8%-71.8% for S.alfredii treatment and 14.1%-58.2% for S.alfredii and strain D-6 combined treatment,respectively,compared with that in the control.The population size of the DDTs-degrading strain,Simpson index (1/D) and soil respiratory rate decreased in the early stage of treatment and then gradually increased,ultimately recovering to or exceeding the initial level.The results indicated that synchronous incorporation of strain D-6 and S.alfredii into soil was found to significantly (p 0.05) enhance the degradation of DDTs in soil and the hyperaccumulation of Cd in S.alfredii.It was concluded that strain D-6 and S.alfredii could be used successfully to control DDTs and Cd in contaminated soil.