Multivariate Statistics of the Pyrolysis Products of High Molecular Components in Pulping Wastewaters to Explain Their Toxicity (6 pp)

Background, Aim and Scope At present, large-scale paper manufacture involves delignification and bleaching by elemental chlorine free (ECF) or totally chlorine free (TCF) processes. The wastewater is purified by secondary treatment (mechanical, chemical and biological) which removes most of the toxic substances from the discharge. However, we found residual toxicity in the high molecular (> 1000 D) matter (HMWM) of the discharge by test of the RET (reverse electronic transfer) inhibition. This fraction consists mainly of polydisperse lignin (LIG) and carbohydrate (CH) macromolecules. Structural units in these molecules are studied by pyrolysis gas chromatography / mass spectrometry (Pyr-GC/MS). In the present work, our aim was to find out those structural units which could explain the RET toxicity of LIG or CH molecules. We compared statistically RET toxicity values of the HMWM samples from treated wastewaters of pilot pulping experiments and intensity variation of the pyrolysis product gas chromatograms of these samples. This application is a novel study procedure. Methods Pyrolysis products (Py-GC/MS results) and inhibition of RET (reverse electronic transport toxicity) as TU50 and TU20 of HMWM (High Molecular Weight Material; Mw > 1000 D) were compared by multivariate statistics. The samples were from laboratory pilot stages of TCF (Totally Chlorine Free) and ECF (Elemental Chlorine Free) manufacture of softwood pulp. Py-GC/MS was done without and with addition of TMAH (Tetra Methyl Ammonium Hydroxide). The name and structure of each abundant fragment compound was identified from its retention time and mass spectrum compared to authentic reference compounds or literature. Four sets of Toxicity Units (TUs) and GC peak areas of the pyrolysis fragments were obtained. The data were normalized by division with LIG (lignin content of each sample). TU values were dependent and the fragment values independent (explanatory) variables in statistical treatments by SPSS system. Separate analyses of correlations, principal components (PCA) and stepwise multiple linear regression (SMLR) were performed from the four sample sets TCF and ECF with and without TMAH. Results and Discussion From the CH fragments, 2-furfural in TCF, and from the LIG fragments, styrene in ECF showed the highest probabilities to originate from source structures of toxicity. Other possible compounds in concern were indicated to be CH fragment 2-methyl-2-cyclopenten-1-one in ECF and LIG fragments 2-methoxy-4-methylphenol, 4,5-dimethoxy-2-methylphenol and 2-methylphenol in TCF.     

陕北黄土高原239+240Pu大气湿沉降历史重建

重建Pu同位素的大气沉降历史是开展Pu示踪应用以及核事故安全评价的重要基础。本研究根据东京年降水量和^239+240Pu年大气沉降数据,并结合经验模型对陕北黄土高原^239+240Pu年湿沉降通量进行初探。结果表明,1957~2005年间研究区^239+240Pu年湿沉降通量在0.000 2~4.116 7 Bq/m²之间,累计湿沉降通量为14.08 Bq/m²;通过与周边土壤剖面的Pu总量对比发现陕北黄土高原Pu同位素的干湿沉降比为1左右。在时间变化上,上世纪60年代初全球大规模核试验导致研究区1963年^239+240Pu湿沉降通量出现峰值,1964~2000年Pu湿沉降通量呈明显减小趋势,2001~2005年亚洲粉尘的地表再悬浮过程使得^239+240Pu年湿沉降通量有所增加。     

Cause of PM2.5 pollution during the 2016-2017 heating season in Beijing, Tianjin, and Langfang, China

To investigate the cause of fine particulate matter (particles with an aerodynamic diameter less than 2.5 µm, PM_2.5) pollution in the heating season in the North China Plain (specifically Beijing, Tianjin, and Langfang), water-soluble ions and carbonaceous components in PM_2.5 were simultaneously measured by online instruments with 1-hr resolution, from November 15, 2016 to March 15, 2017. The results showed extreme severity of PM_2.5 pollution on a regional scale. Secondary inorganic ions (SNA, i.e., NO₃^?+SO₄²+ NH₄⁺) dominated the water-soluble ions, accounting for 30%-40% of PM_2.5, while the total carbon (TC, i.e., OC + EC) contributed to 26.5%-30.1% of PM_2.5 in the three cities. SNA were mainly responsible for the increasing PM_2.5 pollution compared with organic matter (OM). NO₃^? was the most abundant species among water-soluble ions, but SO₄^2- played a much more important role in driving the elevated PM_2.5 concentrations. The relative humidity (RH) and its precursor SO₂ were the key factors affecting the formation of sulfate. Homogeneous reactions dominated the formation of nitrate which was mainly limited by HNO₃ in ammonia-rich conditions. Secondary formation and regional transport from the heavily polluted region promoted the growth of PM_2.5 concentrations in the formation stage of PM_2.5 pollution in Beijing and Langfang. Regional transport or local emissions, along with secondary formation, made great contributions to the PM_2.5 pollution in the evolution stage of PM_2.5 pollution in Beijing and Langfang. The favourable meteorological conditions and regional transport from a relatively clean region both favored the diffusion of pollutants in all three cities.     

京津冀地区典型城市大气细颗粒物碳质组分污染特征及来源

为研究京津冀地区典型城市大气细颗粒物及其碳质组分的时空变化特征及来源,于2016年12月28日—2017年1月22日及2017年7月1—26日,对北京市与石家庄市PM_2.5（细颗粒物）及PM₁（亚微米颗粒物）进行采集,使用DRI（热光碳分析仪）检测PM_2.5与PM₁中ρ（OC）与ρ（EC）,并对其碳质组分来源进行分析.结果表明:①采样期间,冬、夏两季PM_2.5与PM₁中ρ（OC）均为石家庄市采样点远高于北京市采样点;冬季PM_2.5与PM₁中ρ（EC）均为石家庄市采样点高于北京市采样点,夏季则略有不同.②冬季污染日,北京市采样点ρ（PM_2.5）与ρ（PM₁）均为石家庄市采样点的1.08倍,PM_2.5与PM₁中的ρ（OC）分别为石家庄市采样点的1.14和1.12倍,石家庄市采样点PM_2.5与PM₁中ρ（EC）分别为北京市采样点的1.15和1.28倍;冬季重污染日,北京市采样点的ρ（PM_2.5）与ρ（PM₁）分别为石家庄市采样点的1.03和1.04倍,PM_2.5和PM₁中的ρ（OC）分别为石家庄市采样点的1.23和1.22倍,石家庄市采样点PM_2.5和PM₁中的ρ（EC）分别为北京市采样点的1.03和1.16倍.夏季污染日,石家庄市采样点ρ（PM_2.5）与ρ（PM₁）分别为北京市采样点的1.16和1.30倍,PM_2.5与PM₁中ρ（OC）分别为北京市采样点的1.64和2.71倍,两个采样点ρ（EC）相近.③冬、夏两季PM_2.5与PM₁中ρ（SOC）/ρ（OC）均较高,冬季北京市采样点分别为48.09%和54.29%,石家庄市采样点分别为44.98%和48.09%,夏季北京市采样点分别为48.47%和61.50%,石家庄市采样点分别为61.52%和63.55%,表明SOC更易富集于亚微米粒子中.④冬季北京市和石家庄市两个采样点PM_2.5与PM₁中碳质组分均主要来源于生物质燃烧、燃煤和机动车尾气;夏季北京市采样点PM_2.5与PM₁中碳质组分主要来源于机动车尾气,石家庄市采样点PM_2.5与PM₁中碳质组分主要来源于燃煤和机动车尾气.研究显示,北京市和石家庄市两个采样点大气细颗粒物及其碳质组分浓度存在时空分布和污染来源差异.      

典型钢铁企业挥发性有机物排放量测算及组分特征

选取涵盖钢铁炼制全流程的典型企业,综合采用不同核算方法估算比较了该企业挥发性有机物（VOCs）排放结果;并在此基础之上,通过氟聚化合物气袋、SUMMA罐采样及气相色谱质谱联用仪（GC-FID/MS）分析方法,对烧结、焦化、热轧和冷轧等工序废气中VOCs浓度水平及排放特征进行监测.结果表明,整个厂区VOCs年排放量为430.82t,其中工艺有组织排放占66.0%,储罐18.5%;烧结机头和焦炉推焦排放口VOCs及非甲烷总烃（NMHC）浓度高于其他点位;各工序排放的芳香烃占比较高,其中焦化装煤除尘和焦炉推焦排放口芳香烃占90%以上;烧结工序CS₂占比最高（36.6%）,其次为苯和甲苯;焦化工序占比靠前的物种为1,2,4-三甲基苯、邻甲乙苯、1,4-二乙基苯、1,2,3-三甲基苯和1,3,5-三甲基苯等;热轧工序与其他工序有一定区别,车间无组织排放芳香烃和烷烃占比均在35%左右,排放靠前的物种除芳香烃外还有高碳烷烃,如十一烷、十二烷和正丁烷等;冷轧工序有组织和无组织排放主要物种较为类似,均为芳香烃物种,如乙基苯、间/对二甲苯、甲苯、苯和邻二甲苯.不同工艺环节排放物种存在一定差异,但主要以焦化副产物（芳香烃）和烧结燃烧产物（CS₂）为主,建议钢铁行业有针对性地加强浓度高、活性高和毒性大的组分控制.     

预曝气及提取方法对活性污泥胞外聚合物的影响

为了获得更高的胞外聚合物质（EPS）得率及其对污染物的去除效果,比较了活性污泥预曝气时间及2种提取方法（超声法和甲醛+NaOH法）对提取EPS的影响,分析了EPS的荧光组分以及与污染物去除有关的基团差异.结果表明,污泥经过4h预曝气,EPS得率最高;甲醛+NaOH法提取的EPS是超声法的1.5~1.7倍;其中蛋白质、多糖、DNA含量分别是后者的1.4~1.7、0.8~2和2.3~2.7倍.甲醛+NaOH提取法获得的EPS对高岭土的絮凝率和对Cr³⁺的去除率分别高出超声法16%和33%,絮凝率和去除率分别达到了65%和63%.三维荧光光谱分析结果表明,甲醛+NaOH法提取的EPS中芳香蛋白和溶解性微生物代谢产物含量分别是超声法的1.4~1.9倍和1.8~2.4倍;胡敏酸类物质仅大量存在于甲醛+NaOH法提取的EPS中,且腐殖质与Cr³⁺去除率呈显著相关（P<0.01,R²=0.920）.红外光谱分析表明,甲醛+NaOH法提取的EPS中有区别于超声法的特殊基团,其中-OH、-COOH、-NH₂等基团与Cr³⁺发生了配位络合作用.     

柴油烃族组分对柴油机排放的影响

柴油烃族组分可影响柴油的理化特性,从而影响柴油机的燃烧过程,进而对排放产生重要影响.本研究针对烃族组分含量不同的14种柴油,开展了排放特性的试验研究,基于试验结果采用主成分分析法及回归分析法揭示影响柴油机排放性能的关键组分及作用规律,并得到了柴油机排放与关键组分的经验公式,可在一定程度上预测排放特性.分析结果表明,总芳烃是影响柴油机排放的关键组分,当其含量介于5%～17%时,可使NO_x、soot(碳烟)、CO、HC排放均处于较低水平.此外,多环芳烃对柴油机排放有重要影响,其中的苊类、苊烯类对NO_x、碳烟、CO排放的影响作用更为显著,而其他烃族组分与柴油机排放的规律性相对较差.不同工况下,柴油机排放规律有所不同,在低负荷下柴油机排放对总芳烃含量更加敏感.     

轻型汽油车尾气OC和EC排放因子实测研究

选取27辆国3~国5轻型汽油车采用实验室底盘测功机和全流稀释定容采样系统(CVS)开展了尾气颗粒物中有机碳(OC)和无机碳(EC)组分的排放因子实测,分析了启动条件、行驶工况和喷油方式对轻型汽油车OC和EC排放的影响.结果表明,国3~国5轻型汽油车OC平均排放因子分别为(2.09±1.03)、(1.59±0.78)和(0.75±0.31)mg·km-1,EC平均排放因子分别为(1.98±1.42)、(1.57±1.80)和(0.65±0.49)mg·km-1,二者均随排放标准的提升呈显著下降趋势,OC/EC值分别为1.54±0.92、1.53±0.91以及1.47±0.66.OC1、OC2以及EC1和EC2是轻型汽油车排放的最主要碳质组分,分别占15.0%、20.6%、22.2%和21.7%.冷启动条件下轻型汽油车OC和EC排放约为热启动的1.4和1.8倍;高速工况下轻型汽油车OC和EC排放因子约为城区工况的2倍和4倍;缸内直喷(GDI)发动机的OC排放因子与进气道喷射(PFI)发动机接近,但EC排放因子约是后者的1.7倍,随着我国轻型汽油车中GDI发动机日渐普及,其EC排放应当引起密切关注.     

应用元素碳示踪物法解析复杂排放源地区有机碳来源的局限性

元素碳示踪物法(The EC tracer method)因其简单易行被广泛应用于区分有机气溶胶的一次和二次来源.本文以源排放复杂的北京城区(冬夏两季)和山东长岛作为城市和偏远地区的代表,利用气溶胶质谱仪(AMS)和碳黑测定仪等多种仪器的观测结果,基于元素碳示踪物法估算了在这些地区二次源对有机碳的贡献,并将该结果和同观测受体模型正定矩阵因子分析(PMF)的结果进行比较.探讨了北京地区餐饮源和生物质燃烧源对元素碳示踪物法估算二次有机碳的影响.本研究指明了元素碳示踪物法基本假设在源复杂地区应用的局限性,利用该方法对二次有机气溶胶估算会因存在具有较高OC/EC比值的一次排放源,而有一定偏差(例如本论文10%~40%).该研究对其他的元素示踪物法的估算工作具有一定的借鉴意义.     

A TECHNIQUE FOR MEASURING RAINFALL POTENTIAL1

ABSTRACT The roles played by thermodynamic stability and precipitable water in the production of rainfall are of prime importance. These two variables have been combined into a “Rainfall Potential” function by the use of multivariate statistical techniques. Data from weather stations in southern New Mexico and southwest Texas were used in the study. The results appear promising for further investigation, possibly in relation to the occurrence of rare but extremely heavy rains