贵阳市秋冬季PM2.5中重金属污染特征、来源解析及健康风险评估

为掌握贵阳市大气PM_2.5中重金属的污染特征、潜在来源和健康危害,于2017年10月—2018年2月白天(08:00—19:00)、夜间(20:00—翌日07:00)连续采集秋、冬两季大气颗粒物PM_2.5样品(n=202),采用电感耦合等离子体质谱(ICP-MS)法,检测样品中10种重金属(Pb、Cd、Cr、As、Zn、Mn、Co、Ni、Cu和V)含量,分析其昼夜质量浓度特征及变化规律,运用PMF(正定矩阵因子分析)模型和HMHR(健康风险评价模型)分别探讨其来源及健康风险.结果表明:①秋、冬两季大气颗粒物ρ(PM_2.5)日均值分别为(53±18)(62±20)μg/m3,均低于GB 3095—2012《环境空气质量标准》二级标准(75 μg/m3);ρ(As)、ρ(Zn)和ρ(Mn)均呈冬季高于秋季的特征,其他元素变化不明显.②白天ρ(PM_2.5)为(61±20)μg/m3,稍高于夜间〔(58±24)μg/m3〕;ρ(Pb)白天低于夜间,ρ(Ni)、ρ(Mn)、ρ(Zn)和ρ(Cu)则白天高于夜间,其他元素昼夜质量浓度无明显差异.③PMF模型分析表明,交通污染、燃煤、工业冶金和土壤扬尘是采样期间10种重金属的主要来源,其贡献率分别为39%、37%、14%、10%.④HMHR结果表明,Cd和Mn对儿童存在非致癌风险,其他重金属元素对人群无非致癌风险.致癌元素As、Cr和Cd的致癌风险值介于4.3×10-6~4.4×10-5之间,对人群可能存在致癌风险;而Ni和Co的致癌风险值均低于可接受水平(10-6).研究显示,贵阳市秋、冬两季PM_2.5中重金属污染水平整体较低,交通污染和煤炭燃烧是其主要来源,重金属元素中Cd、Mn、As和Cr对人群存在一定的健康风险.      

贵州茂兰喀斯特森林不同演替下土壤真核微生物多样性

真核微生物是茂兰喀斯特森林土壤微生物中的重要组成部分,在生态系统物质循环和能量流动中扮演着重要角色.为了解茂兰喀斯特森林不同演替阶段下土壤真核微生物群落组成及其多样性,利用18S rDNA高通量测序技术研究了原生林(YSL)、灌木林(GML)、灌木丛(GMC)和草地(CD)这4种演替阶段下土壤真核微生物群落多样性.结果表明,在不同分类水平下,不同演替阶段土壤真核微生物群落组成相似.α多样性指数存在显著差异, Shannon指数与Simpson指数在不同演替阶段表现为:YSLGMCGMLCD. NMDS分析表明不同演替阶段土壤真核微生物群落结构存在差异; LEfSe分析表明,YSL中差异指示种数量高于GML、GML和CD.本研究结果为研究不同演替阶段下土壤真核微生物提供了理论基础.     

贵阳市春、冬季大气颗粒物中铂族元素的污染特征

本文在贵阳市市中心区和郊区设置两个采样点位,采集春季和冬季PM_(10)、PM_(2.5)样品,在封闭溶样装置中采用HF和王水消解,利用电感耦合等离子体质谱法测定颗粒物中铂族元素的含量,研究了大气颗粒物中铂族元素的污染特征。结果表明,市中心区样品中铂族元素的浓度大于郊区,其含量与交通密度有关;与Pt和Rh相比,颗粒物中Pd的浓度更高,Pd具有较大的溶解性,可能会给人类健康带来更严重的危害;颗粒物中铂族元素的浓度呈现季节性变化,冬季大于春季。与国外其他城市相比,贵阳市大气颗粒物中铂族元素的污染程度较低,但这种潜在的重金属污染应引起重视。     

利用PARAFAC及SOM研究不同来源及粒径胶体的三维荧光光谱特征

利用三维荧光光谱法(3D-EEM)结合平行因子分析(PARAFAC)和自组织神经网络分析(SOM),解析了不同来源水体中不同粒径胶体的荧光特性,同时与挑峰法进行比较,以期寻找一种更好的分析天然胶体来源、粒径、荧光特性间关系的方法.基于PARAFAC模型,研究区水体中不同粒径胶体共解析出2个类腐殖质荧光峰(C1和C3)及3个类蛋白荧光峰(C2、C4和C5).其中,300 k Da~1μm分级胶体荧光强度最高,C1、C2、C3组分的荧光强度随粒径增大而增强,C4、C5组分的荧光强度随粒径增大而减弱.不同来源胶体(生活污水:进水和出水;农业污水:大盈和天恩桥;天然水体:吴淞口)的荧光强度变化大致规律为:吴淞口进水大盈天恩桥出水.SOM分析结果与PARAFAC一致,且可视化程度更高,但EEM-SOM模型存在输入变量多、兼具挑峰法缺点的问题.而PARAFAC-SOM模型不仅兼具了前两者的优点,还具有输入变量少、运行时间短、可靠性高等优点.同时,该模型还成功应用于胶体其他理化参数的分析(Parameters-SOM模型),使得前期工作结果系统性更强、更直观.因此,PARAFAC-SOM模型是相对较好的分析天然胶体来源、粒径、荧光特性间关系的方法.     

废物焚烧厂烟气中PCDD/Fs和PCNs的排放特征

采用同位素内标稀释高分辨气质联用分析法,对废物焚烧厂的烟气样品PCDD/Fs和PCNs进行了测定,分析了其排放特征以及相关性,为有组织排放的PCDD/Fs和PCNs的控制提供理论依据.实验结果表明,空白实验中未发现明显的背景干扰;样品中PCDD/Fs的采样内标回收率范围为74.0%~90.1%,提取内标的回收率范围为53.3%~120.0%,均符合US EPA23和CHN HJ77.2-2008的质量控制标准;PCDD/Fs的同系物浓度均随着氯取代数目的增加而增加,而PCNs同系物则随着氯取代数目的增加表现出先增大后减小的规律.同系物之间的皮尔森相关系数分析结果可知,这两类污染物相邻同系物相关性系数明显大于非相邻同系物相关性系数,表明低氯代同系物可能是生成高氯代同系物的一个重要途径.此外,PCNs和PCDD/Fs同系物的线性相关分析结果表明,一些PCNs化合物（PeCN、HxCN、HpCN、OCN）与某些PCDD/Fs（OCDD、PeCDF、HxCDF、HpCDF）具有良好的相关性（R²=0.55~0.78）,由此推断在废物焚烧过程中这些同系物可能具有相类似的生成机制.     

磁性Fen+@GO非均相Fenton催化氧化亚甲基蓝

采用化学共沉淀法制备了磁性Feⁿ⁺@GO（MFGO）纳米复合材料,并将其用于非均相Fenton催化氧化亚甲基蓝（MB）.扫描电镜、透射电镜和光电子能谱分析表明,催化活性粒子（Feⁿ⁺/铁氧化物）成功负载在GO表面.实验研究了pH值、H₂O₂初始浓度、催化剂投加量等因素对MB降解效果的影响.结果表明,H₂O₂、MFGO和H₂O₂+MFGO体系在反应120min后,MB降解率分别达到7.83%、25.58%和99.19%;在优化条件为H₂O₂浓度0.79mol/L、MFGO用量0.75g/L、pH值8时,MB降解率可达99.90%;在pH值为3~11范围内,MB降解率均在99%以上;MFGO经过6次重复使用后对MB的降解率仍可达到95.08%,是一种pH值响应宽、可磁分离回收的新型非均相催化剂.     

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.     

Baosteel emission control significantly benefited air quality in Shanghai

As the largest iron and steel producer in China, a part of Baosteel moved out of Shanghai deserves close attention due to its environmental impact. To understand the effect of Baosteel emission control on air quality in Shanghai, daily PM_(10), PM_(2.5), SO_2, NO_2 and CO were measured from 2010 to 2016. Concentrations of pollutants in Baoshan District presented a decreased trend during 2010–2016, with a reduction rate of 28.6% for PM_(10), 67.3% for SO_2, 8.6% for NO_2 and 42.0% for CO. However, fine particle pollution in Baoshan District during 2012–2016 seems to become more prominent, with PM_(2.5) concentration of 47 ± 28,45 ± 33, 38 ± 24, 54 ± 41 and 51 ± 34 μg/m3, respectively, indicating a slight increase of 8.5%in PM_(2.5). Concentrations of PM_(10) and CO decreased by 12.5% and 33.8% in the second half year in 2016(compared with that in 2015) probably due to closure of blast furnace of Baosteel. Baosteel was identified as the largest pollution source in Baoshan District.Emission from Baosteel accounted for 58.0% of SO_2, 43.6% of NO_2 and 79.3% of dust in total emission from Baoshan District during 2010–2015. Meanwhile, pollutant emission and coal consumption from Baosteel decreased by 52.0% for SO_2, 40.1% for NO_2, 15.7% for dust and22% for coal consumption. Energy consumption in Baoshan District reduced by 31% from2011 to 2015. Air quality improvement in Shanghai was attributed to local emission reduction, together with regional air quality improvement.     

Removal of nutrients and veterinary antibiotics from swine wastewater by a constructed macrophyte floating bed system

The potential of three varieties of Italian ryegrass (Lolium multiflorum Lam.), Dryan, Tachimasari and Waseyutaka, to improve the water quality of swine wastewater was evaluated using a constructed macrophyte floating bed system. With respect to reductions in levels of nutrients, chemical oxygen demand (COD), and sulfonamide antimicrobials (SAs, including sulfadiazine, sulfamethazine, and sulfamethoxazole), Dryan performed better than Tachimasari and Waseyutaka. For Dryan, total N was reduced by 84.0%, total P by 90.4%, COD by 83.4% and sulfonamide antimicrobials by 91.8–99.5%. Similar results were observed for Tachimasari and Waseyutaka. The results indicated that the treatment of swine wastewater using the constructed macrophyte floating bed system was effective in the removal of nutrients and veterinary antibiotics.