二龙湖表层水体有色溶解有机物的光学特性及来源

CDOM（colored dissolved organic material,有色溶解有机物）的光学特性可反映水体中内源物质与外源物质的比例,为了解二龙湖受到上游来水所含污染物的影响,利用荧光区域一体化技术和荧光指数分析水体中CDOM的荧光特性,进而判定水体污染状况,并结合CDOM荧光组分与水质参数之间的关系,探讨了不同季节二龙湖水体中CDOM光学特性在时空分布上的差异性以及CDOM的组成与来源.结果表明:①水相中CDOM表现出明显的季节性差异.其中,光谱斜率S_g（275~295 nm）和E_{250 nm:365 nm}〔a_CDOM（250）/a_CDOM（365）〕均表现为丰水期>平水期>枯水期,SUVA_{254 nm}表现为枯水期>平水期>丰水期.②水体中的荧光组分以外源组分R3（富里酸类物质）和R5（腐殖酸类物质）为主,在枯水期、丰水期和平水期分别占总荧光强度的70.0%、60.4%和51.3%.③在丰水期、枯水期、平水期,FI_{310 nm}平均值均大于0.8,FI_{370 nm}平均值均小于1.4,表明在3个水文期,微生物活动带来的内源CDOM在二龙湖南部较为明显.④ρ（DOC）（dissolved organic carbon,溶解性有机碳）与CDOM的荧光组分R2（色氨酸类组分）、R4（可溶性微生物副产物组分）和R5（腐殖酸类组分）均具有较好的相关性,相关系数（R）分别为0.71、0.80、0.73,表明DOC主要源于微生物代谢的可溶性副产物及浮游植物的降解.研究显示:水体中CDOM主要组成为内源的色氨酸与微生物蛋白质类副产物以及外源的富里酸类与腐殖酸类有机物;同时,由于冰冻、降水、生活污水排放、农业废水和水生植物等因素,导致湖泊中的CDOM的组分与来源十分复杂.      

土壤冻融对溶解性有机质与菲结合的影响

以沈阳市公园土壤和道路边土壤中的溶解性有机质(DOM)为研究对象,利用荧光淬灭法测定DOM与菲的结合常数(K),考察了冷冻温度、融化温度、冷冻时间和冻融次数对其光谱学特性及其与菲的结合常数(K)的影响,并结合相关性矩阵分析K与其他参数的关系.结果表明:冻融处理条件下,K值与溶解性有机碳含量(DOC)显著负相关(p0.01),与254 nm处的紫外吸光系数(a_(254))和单位浓度DOC的254 nm的紫外吸光值(SUVA)显著正相关(p0.01).城市公园土壤DOM和城市道路边土壤DOM的K值都是3.5×10~4L·kg~(-1),经过冷冻温度、冷冻时间和冻融次数相同的冻融处理后,城市公园土壤DOM的K值始终高于城市道路边土壤DOM,这是由于冻融导致城市土壤DOM的芳香性高于城市道路边土壤DOM,而分子量小于城市道路边土壤DOM.经过冻融作用二者的K值变化范围分别为1.6×10~5～8.4×10~5L·kg~(-1)和1.5×10~5～3.7×10~5L·kg~(-1),冻融作用使二者的K值都增大一个数量级.这一方面会增强固相土壤中多环芳烃的溶出和迁移,另一方面也会降低多环芳烃的生物可利用性.     

AAO-MBR工艺污水处理系统中消毒副产物前体物变化规律

为探究DBPs（消毒副产物）前体物在污水处理过程中的变化情况,采用超滤膜和XAD大孔吸附树脂将AAO-MBR工艺沿程出水中DOM（溶解性有机物）进行分离,并利用3D-EEM（三维荧光光谱）对分离前后水样进行表征,同时测定DBPFP（消毒副产物生成势）.结果表明:①沉砂池出水具有较低的C-DBPFP（含碳消毒副产物生成势）;经过AAO和MBR后,由于微生物代谢作用生成的疏水性SMPs（微生物代谢产物）类物质（为主要的C-DBPs前体物质）包含较多不饱和键,导致C-DBPFP增加.②沉砂池出水的N-DBPFP（含氮消毒副产物生成势）较低,但经过AAO后生成的小分子物质（为主要的N-DBPs前体物）导致N-DBPFP增加;经过MBR后由于SRT（污泥停留时间）和污泥浓度的增加造成小分子物质减少,致使N-DBPFP降低.③市政污水经过AAO后,C-DBPs和N-DBPs前体物分别增加了90.9%和7.3%;而MBR具有较高的DOC去除率（74.4%）,去除了56.8%的C-DBPs前体物和78.1%的N-DBPs前体物.研究显示,AAO-MBR工艺对市政污水中C-DBPs和N-DBPs前体物有较好地去除效果.      

城郊与城镇河流中溶解性有机质与重金属的相关性

溶解性有机质(dissolved organic matter,DOM)在水体环境中广泛存在,对重金属在水环境中的环境行为有重要影响.本研究为探讨DOM与重金属的相关性,以宁波市城郊流域樟溪和城镇流域芦江为例,利用三维荧光技术分析不同城镇化梯度下河流水体溶解性有机质(DOM)的结构组成特征,分析DOM各项参数与重金属之间的相关性.结果表明,城镇化程度较高的河流水体具有较高的DOC、有色溶解性有机质(CDOM)和荧光溶解性有机质(FDOM)浓度;城郊流域与城镇流域水体中DOM均含有4个荧光峰,类富里酸荧光峰A和C以及类蛋白荧光峰B和T,且城镇流域水体荧光峰B和T的强度显著高于城郊流域,DOM腐殖化程度与芳香性也具有同样的趋势;城镇流域水体中重金属As、Cu和Mn浓度显著高于城郊流域.DOM与重金属的相关性结果表明,城镇河流中DOM与Cu、Cr、Mn、As、Zn和Pb都存在显著的正相关关系,而城郊河流中DOM只与Mn、Pb和Cu呈显著正相关,与其它重金属相关性不明显.总之,城镇化水平影响河流水体中CDOM的浓度和性质,而CDOM浓度和性质与重金属的行为密切相关.     

Relating Cd2 + binding by humic acids to molecular weight: A modeling and spectroscopic study

Molecular weight(Mw) is a fundamental property of humic acids(HAs), which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid(HA) extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna(NICA-Donnan) models combined with fluorescence excitation-emission matrix(EEM) quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd~(2+) to Mw fractions of HA followed the order UF1( 5 kDa) UF2(5–10 kDa) UF4( 30 kDa) UF3(10–30 kDa). Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd~(2+) among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd~(2+) to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.     

Polar organic tracers in PM2.5 aerosols from an inland background area in Southwest China: Correlations between secondary organic aerosol tracers and source apportionment

PM_(2.5) aerosol samples were collected over 12 hr and 24 hr intervals in an inland background area, Gongga Mountain National Nature Reserve(hereafter shortened to Gongga), during the summer of 2011. Polar organic tracers, inorganic ions and meteorological data were measured. The purpose of this work was to investigate the variation patterns, formation and sources of the secondary organic aerosol tracers in the studied atmosphere. The average concentrations of isoprene oxidation products, α-pinene oxidation products, β-caryophyllinic acid, sugars, sugar alcohols and anhydrosugars were 88.6 ± 106.1, 3.6 ± 5.7,0.13 ± 0.30, 13.6 ± 13.1, 31.9 ± 31.4 and 14.8 ± 10.7 ng/m3 respectively in all aerosol samples.The aged α-pinene second organic aerosol(SOA) tracers(i.e., 3-hydroxyglutraric acid(3 HGA), 3-hydroxy-2,2-dimethylglutaric acid(HDMGA), 3-acetylpentandioic acid(APDA) and 3-methyl-1,2,3-butanetricarboxylic acid(MBTCA)) correlated significantly with each other in the 24 hr PM2.5 aerosol samples, indicating that OH· is the major factor controlling the formation of these α-pinene SOA tracers. Using the positive matrix factorization(PMF) model and the tracer-based source apportionment method, we calculated that isoprene oxidation products, α-pinene oxidation products, sesquiterpene oxidation products, biomass burning, fungi spores and anthropogenic SOA accounted for 21.9% ± 5.5%, 8.4% ± 2.1%, 3.0% ± 0.7%, 5.2% ± 5.3%, 5.0% ± 6.2% and 31.4% ± 7.8% of organic carbon respectively during the sampling period.     

PM2.5 source apportionment in a French urban coastal site under steelworks emission influences using constrained non-negative matrix factorization receptor model

The constrained weighted-non-negative matrix factorization(CW-NMF) hybrid receptor model was applied to study the influence of steelmaking activities on PM_(2.5)(particulate matter with equivalent aerodynamic diameter less than 2.5 μm) composition in Dunkerque,Northern France. Semi-diurnal PM_(2.5)samples were collected using a high volume sampler in winter 2010 and spring 2011 and were analyzed for trace metals, water-soluble ions, and total carbon using inductively coupled plasma – atomic emission spectrometry(ICP-AES),ICP- mass spectrometry(ICP-MS), ionic chromatography and micro elemental carbon analyzer. The elemental composition shows that NO_3~-, SO_4~(2-), NH_4~+and total carbon are the main PM_(2.5)constituents. Trace metals data were interpreted using concentration roses and both influences of integrated steelworks and electric steel plant were evidenced. The distinction between the two sources is made possible by the use Zn/Fe and Zn/Mn diagnostic ratios. Moreover Rb/Cr, Pb/Cr and Cu/Cd combination ratio are proposed to distinguish the ISW-sintering stack from the ISW-fugitive emissions. The a priori knowledge on the influencing source was introduced in the CW-NMF to guide the calculation. Eleven source profiles with various contributions were identified: 8 are characteristics of coastal urban background site profiles and 3 are related to the steelmaking activities. Between them,secondary nitrates, secondary sulfates and combustion profiles give the highest contributions and account for 93% of the PM_(2.5)concentration. The steelwork facilities contribute in about 2%of the total PM_(2.5)concentration and appear to be the main source of Cr, Cu, Fe, Mn, Zn.     

太湖水体溶解性有机质荧光特征及其来源解析

利用三维荧光光谱(3DEEM)-平行因子分析(PARAFAC)技术,通过野外现场调查和室内模拟实验,分析富营养化湖泊(太湖)水体溶解性有机质(DOM)组成结构、分布规律及其来源,进一步研究藻类和水生植物残骸腐烂分解以及沉积物释放对水体DOM荧光组成特征的影响.结果表明:1太湖水体各个湖区DOM主要以类色氨酸物质(T1、T2峰)为主,竺山湾还存在类腐殖质和类富里酸物质,其荧光指数(f450/500)为1.53±0.06,接近陆源f450/500值(1.4),DOC浓度全湖最高((7.13±2.45)mg·L-1),兼具陆源与生物来源的双重特性.2太湖藻类DOM组成丰富,出现了7种荧光组分,主要为类腐殖质、类富里酸和类蛋白物质(包括类色氨酸和类酪氨酸),藻类腐烂分解后,紫外区类色氨酸T2峰和类酪氨酸B2峰消失,其他类蛋白物质和部分易降解的类富里酸物质向水体中释放,其中A峰和C峰所代表的类富里酸物质降解率较高,分别降解了70.3%和41.0%.3水生植物DOM以类腐殖酸物质为主,其残骸腐烂分解后DOM由陆源类腐殖质向类腐殖酸物质转化.4沉积物DOM出现了5类荧光峰,兼具外源污染的类富里酸荧光C峰和A峰,同时含有生物来源的B1、B2、T2类蛋白荧光峰,随其降解时间的增长,T2荧光峰消失,B1、B2荧光物质降解率分别高达86.5%和82.5%,而C峰和A峰分别上升25.1%和1.5%,沉积物降解过程中大量类蛋白物质向上覆水体中释放,同时部分类蛋白物质向着更稳定的类富里酸物质转化.因此,外源输入和内源负荷(藻类和水生植物残骸腐烂分解以及沉积物释放等)对湖泊水体DOM组成结构以及富营养化过程具有重要影响.     

Identifying the major fluorescent components responsible for ultrafiltration membrane fouling in different water sources

Three-dimensional fluorescence excitation–emission matrix(EEM) coupled with parallel factor analysis(PARAFAC) was performed for a total of 18 water samples taken from three water sources(two lakes and one wastewater treatment plant(WWTP) secondary effluent),with the purpose of identifying the major ultrafiltration(UF) membrane foulants in different water sources. Three fluorescent components(C1, C2 and C3) were identified,which represented terrestrially derived humic-like substances(C1), microbially derived humic-like substances(C2), and protein-like substances(C3). The correlations between the different fluorescent components and UF membrane fouling were analyzed. It was shown that for the WWTP secondary effluent, all three components(C1, C2 and C3) made a considerable contribution to the irreversible and total fouling of the UF membrane.However, for the two lakes, only the C3 exhibited a strong correlation with membrane fouling, indicating that the protein-like substances were the major membrane foulants in the lake waters. Significant attachment of C1, C2 and C3 to the UF membrane was also confirmed by mass balance analyses for the WWTP secondary effluent; while the attachment of C1 and C2 was shown to be negligible for the two lakes. The results may provide basic formation for developing suitable fouling control strategies for sustainable UF processes.     

HfB2-HfC-SiC 改性 C/C 复合材料的超高温烧蚀性能研究

目的制备HfB_2-HfC-SiC复相陶瓷改性C/C复合材料,并探究该材料的超高温烧蚀性能。方法采用化学气相渗透结合前驱体浸渍热解工艺制备HfC-SiC复相陶瓷改性C/C复合材料(C/C-HfC-SiC)和HfB_2-HfC-SiC复相陶瓷改性C/C复合材料(C/C-HfB_2-HfC-SiC),采用大气等离子烧蚀实验研究材料的超高温烧蚀性能。结果C/C-HfC-SiC和C/C-HfB_2-HfC-SiC复合材料2200℃线烧蚀率分别为1.54×10~(-3),1.38×10~(-3)mm/s。结论复合材料具有独特的微结构特征,亚微米级的HfB_2和HfC基体均匀弥散分布在SiC基体中。复合材料表面原位生成的液相SiO_2和固相HfO_2复合氧化物膜,既可以抵抗高速气流的冲蚀,又可以抵抗氧化性气氛的向内扩散,是复合材料具有优异超高温抗烧蚀性能的主要原因。