腐殖酸三维荧光光谱特性研究

腐殖质的荧光特性被广泛用来解析其在各种天然环境中的来源及分布.由于荧光光谱分析具有灵敏度高,选择性好,且不破坏样品结构的优点,非常适合用来研究腐殖质的结构和官能团等特征.利用三维荧光激发-发射光谱研究了 Fluka腐殖酸的荧光光谱特性,结果显示,离子强度(0～0.05 mol/L KClO4)对 Fluka腐殖酸的三维荧光光谱特性影响非常小,而腐殖酸的浓度(5～100 mg/L)和溶液 pH(2～12)对其三维荧光光谱特性影响显著.当腐殖酸浓度增大时,荧光峰出现明显红移现象.荧光强度一般随着 pH的升高而增大,当 pH大于 10后呈下降趋势,我们从垃圾渗滤液溶解有机质的实验结果中也得到相同结论;在浓度为 50 mg/L和 100 mg/L的 Fluka腐殖酸中,荧光峰 B(fulvic-like)的荧光强度却在 pH=5.0左右时达到最大值,与前人报道的土壤富里酸的行为一致,质子化常数 lgK′ HL分别为 3.57和 3.13,与二羧基化合物接近,说明荧光峰 B可能与 Fluka腐殖酸结构中的羧基有关;荧光峰 A与荧光峰 B的荧光强度比值 r(A/B)在 0.61～2.59之间,并且在 pH=2～11范围内, r(A/B)与 pH具有较好的线性相关关系,表明荧光峰 A和荧光峰 B随着 pH值的改变有着相同的变化趋势.     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

腐泥型煤二次生烃热解模拟的荧光特征

通过对4块腐泥型煤原样及热解模拟残渣样的荧光特征的研究,对腐泥煤二次生烃特征加以探讨,得出主要结论为:(1)当开始二次生烃时,将出现蓝移现象,蓝移现象标志着二次生烃的开始;(2)蓝移现象发生的起始位置(镜质组反射率为标志)及蓝移现象的强度与样品的原始成熟度有密切关系,伴随着原始成熟度的提高,蓝移现象发生的成熟度位置将逐渐后移,其与初始成熟度的差值将先增大后减小,增大与减小的转折点推测位于1.4 6%~1.80%之间。      

大九湖泥炭沼泽源铁有机配合物的络合稳定性及其生态环境意义

为了研究泥炭沼泽源铁有机配合物的络合稳定性,利用pH电位滴定法和荧光淬灭滴定法测定了大九湖泥炭沼泽中不同分子量段的DOM和Fe2+、Fe3+的络合稳定常数.pH电位滴定法结果（4.0~6.1）和荧光淬灭滴定法（1.5~4.1）差异较大,这与高pH条件下OH被脱质子化及Fe2+的氧化有关.相对而言,pH滴定法更适用于探究不同分子量段DOM与铁的络合稳定性,荧光淬灭法不改变样品酸碱条件,更适于研究不同价态铁与DOM的络合稳定性.研究结果表明:DOM与Fe3+的络合稳定常数大于Fe2+,低分子量段（< 3 kDa）的DOM与Fe2+、Fe3+的络合稳定常数更大.泥炭沼泽源铁有机配合物具有较好的络合稳定性,分子量相对较小的DOM与铁的络合能力更强.即便Fe2+氧化为Fe3+,仍能与DOM络合并保持较强的稳定性,这有利于陆源溶解性铁向水生态系统的输出.沼泽源铁有机配合物的络合稳定性还会影响铁的生物可利用性.      

洱海沉积物孔隙水中溶解有机质的三维荧光光谱特征

文章应用三维荧光光谱技术对洱海沉积物孔隙水中的溶解有机质进行了研究。结果表明,所有样品均含有4个明显的荧光峰,其中A和C为类腐殖酸荧光,B和D为类蛋白荧光。荧光强度在沉积物-水界面特别强,在1cm处急剧下降,之后随着沉积深度呈上升趋势。孔隙水溶解有机质均具有强的类蛋白荧光,揭示了溶解有机质中含有大量色氨酸、酪氨酸等芳环结构的类蛋白物质,并且在早期成岩过程中随着沉积深度呈积累趋势;类蛋白荧光与类腐殖酸荧光之间具有一定的相关关系,r(A,C)值在0.94-1.79之间,随着沉积深度逐渐下降,r(D,B)值在0.9-1.75之间,与r(A,C)值极为接近,且随着沉积深度有着类似的变化趋势,说明在洱海沉积物孔隙水中,r(D,B)与r(A,C)之间具有一定的相关性。     

水质监测中激光诱导荧光遥测技术的应用

激光诱导荧光(LIF)遥测是针对大面积水域富营养化状况进行原位、实时、快速测量的一种先进的监测技术。利用自行研制的水体污染LIF遥测系统对太湖水域进行了一次较为全面的测量,以测得的溶解有机物(DOM)荧光因子、瑞利散射因子和叶绿素a荧光因子分别代表各测量点的DOM浓度、浊度和叶绿素a浓度。同时以Skalar三维荧光成像仪测量各点DOM浓度,多参数水质分析仪测量浊度和叶绿素a浓度。对比分析了LIF遥测系统测量DOM荧光因子、瑞利散射因子和叶绿素a荧光因子与DOM浓度、浊度和叶绿素a浓度关系。结果表明LIF系统测得的DOM因子与三维荧光成像仪测量的DOM浓度值一致性较好(R=0.88733),而瑞利散射因子和叶绿素a荧光因子与多参数水质测量仪测得浊度值和叶绿素a浓度值线性相关性较差,相关系数分别为-0.39185和0.4552。对上述差异产生的可能原因进行了讨论,并阐述了LIF遥测技术在水质监测中的应用前景和潜在的应用限制。     

NaCl侵蚀环境下水泥固化铬污染土的强度及淋滤特性

日益严重的环境污染问题导致土壤中的重金属离子越来越多,这不仅使得土的工程性质受到影响,而且有害重金属离子的渗出也会威胁人类的健康。目前常采用水泥固化技术（S/S法）来处理重金属污染土。但当地下水中富含侵蚀性盐离子时,固化后的重金属污染土会受到影响,进而改变其强度及重金属离子的滤出特性。通过系统的室内试验,对水泥固化铬污染土在NaCl溶液浸泡后的强度特性及重金属离子的滤出特性进行了研究。试验结果表明,水泥固化铬污染土的无侧限抗压强度随NaCl溶液浓度的增加而减小,而随浸泡时间的增加呈先减小后增大的趋势,浸泡7 d时最小。毒性特征沥滤试验（TCLP）结果显示,浸出液中Cr3+浓度随NaCl浓度增加而增大,随浸泡时间增加而减小;而浸出液的pH值随NaCl浓度增加而减小,随着浸泡时间的增加呈先减小后增大的趋势,浸泡7 d时最小;浸出液的pH值在4.0～5.5范围内时,Cr3+滤出量随pH值增大而减小。     

NaCl侵蚀环境下水泥固化铬污染土的强度及淋滤特性EI北大核心CSCD

日益严重的环境污染问题导致土壤中的重金属离子越来越多,这不仅使得土的工程性质受到影响,而且有害重金属离子的渗出也会威胁人类的健康。目前常采用水泥固化技术（S/S法）来处理重金属污染土。但当地下水中富含侵蚀性盐离子时,固化后的重金属污染土会受到影响,进而改变其强度及重金属离子的滤出特性。通过系统的室内试验,对水泥固化铬污染土在NaCl溶液浸泡后的强度特性及重金属离子的滤出特性进行了研究。试验结果表明,水泥固化铬污染土的无侧限抗压强度随NaCl溶液浓度的增加而减小,而随浸泡时间的增加呈先减小后增大的趋势,浸泡7d时最小。毒性特征沥滤试验（TCLP）结果显示,浸出液中Cr3＋浓度随NaCl浓度增加而增大,随浸泡时间增加而减小;而浸出液的pH值随NaCl浓度增加而减小,随着浸泡时间的增加呈先减小后增大的趋势,浸泡7d时最小;浸出液的pH值在4.0～5.5范围内时,Cr3＋滤出量随pH值增大而减小。     

离子强度对苝与溶解有机质疏水性组分相互作用的影响

自然界水体(如地下水、湖泊、河流及海洋)中的溶解有机质(DOM)因具有显著的生态及环境功能而受到人们的广泛关注:DOM能够影响环境中污染物的命运,比如疏水性有机污染物(HOCs)与天然有机质结合后,其迁移途径、生物可利用性和毒性受到明显的控制,其对环境中生物的危害性减弱。本文运用荧光猝灭法测定了多环芳烃苝(perylene)与提取自红枫湖天然水体的DOM有机组分,计算了苝与DOM有机组分相互作用的分配系数(KDOC),探讨了影响相互作用的因素以及水体离子强度对分配系数的影响。研究认为,红枫湖DOM有机组分对多环芳烃苝的吸附能力与其芳香结构单元有很强的相关性,log KDOC值与有机组分在280 nm处的摩尔吸收(ε280)和分子质量有线性度较高的正比关系。一般而言,离子强度对分配系数的影响比较复杂,就总体趋势而言,增加离子强度有利于对PAHs吸附能力的提高。     

油页岩对钴离子的吸附性能研究

油页岩中因含有大量的黏土矿物而对金属离子具有一定的吸附能力.采用静态吸附法对油页岩吸附钴离子的影响因素及吸附动力学进行了研究.结果表明,油页岩粒度、溶液浓度、溶液pH值、吸附时间等均对吸附性能有一定影响.油页岩对钴离子的吸附量随样品粒径的减小而增大;随着钴离子初始浓度的增加,油页岩对钴离子的吸附总量增加;溶液pH值在3~8范围内,油页岩对钴离子的吸附量和吸附率随着pH值的增大呈上升趋势.通过吸附动力学研究发现,油页岩对钴离子的吸附过程符合准二级动力学过程和粒子内扩散机理.     

Effects of water chemistry and concentrations of dissolved organic matter on its fluorescence characteristics and molecular conformation

Previous studies showed that water chemistry and concentrations of dissolved organic matter (DOM) could affect its molecular conformation and binding characteristics with hydrophobic organic contaminants (HOCs). However, the conformational change of DOM resultant from water chemistry and concentrations of DOM was not extensively investigated; therefore, the contradictory reports regarding the binding property with HOCs were available in literature. In this study, the effects of ionic strength, pH and DOM concentrations on the fluorescence properties of two humic acids (HA), namely Fluka HA and Amherst HA, were investigated by three-dimensional excitation-emission matrix fluorescence spectroscopy (3DEEM) and steady-state fluorescence polarization (FP) techniques. The results not only corroborated previous observations obtained by other investigators, but revealed some new information about the fluorescence properties and molecular conformation of the humic acids under different water chemistry and DOM concentration conditions, which could shed light on its binding mechanisms and binding properties with HOCs.     

Fluorescence excitation-emission matrix characterization of a commercial humic acid

Excitation-emission matrix fluorescence spectroscopy (EEM) has been widely used to elucidate the origin and structure of humic substances in natural environments. Due to its high sensitivity, good selectivity and non-destructive advantage, the EEM was applied to characterizing a commercial Fluka humic acid (FHA). The results showed that the EEMs of FHA has several Ex/Em peaks. Ionic strength (0-0.05 moL/L KClO4 ) exerted little effect on the fluorescence properties of FHA, while the concentrations (5-100mg/L) of FHA and pH (2-12 ) had significant effects. A red shift in the longer wavelength peak region was observed when the coneentrations or pH values increased. The fluorescence intensity increased with increasing pH, but slightly decreased in the case of pH = 5.0. The protonation constants ( lgK^ HL ) of peak B were calculated to be 3.57 and 3.13, indicating that peak B was due to carboxyl groups. The r(A/B) values range from 0.61 to 2.59. A strong linear relationship between r(A/B) and pH was also observed. This indicates that the fluorescence peaks A and B posses similar inherent fluorescence characteristics.     

Molecular Weight Distribution of Dissolved Organic Matter in Lake Hongfeng Determined by High Performance Size Exclusion Chromatography （HPSEC） With On-Line UV-Vis Absorbance and Fluorescence Detection

1IntroductionDissolvedorganicmatter (DOM)isamixtureoforganicsubstancesconsistingmainlyofhighmolecularweightpolymericcompounds (KenandLee,1 974) .Itplaysanimportantroleincarboncyclingandbiogeochemicalmobilizationoftracemetalsandorganiccompoundsintheaquaticenvi ronment (BeffleandLeppard ,1 995) .InrecentyearsmanyresearchershavepaidattentiontothesecomplexesbasedontheMWDofDOM ,sincethefateandtransportoftracechemicalsareinfluencedbyitsmolecularsize (Chiouetal.,1 986) .Themolecularweightorfrac…     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

N-15 NMR spectra of naturally abundant nitrogen in soil and aquatic natural organic matter samples of the International Humic Substances Society

The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS ¹⁵N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by ¹⁵N NMR. Liquid state ¹⁵N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection (¹H–¹⁵N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.     

Interaction of Cr(III) with the humus acids of soil,water, and bottom sediments

The interaction of Cr(III) with humus acids [fulvic (FA) and humic (HA) acids] was studied in the systems Cr(III)-FA, Cr(III)-HA, and Cr(III)-FA-HA. Chromium(III) reacts with FA extracted from the headwaters of the Moscow River and from the Krapivenka River (a tributary of Lake Seliger) to form a highly soluble high-molecular-weight Cr(III)-hydroxofulvate complexes with \(\bar \beta _{11} \) = 1.93 × 10⁶ and 5.70 × 10⁶, respectively. Humic acids extracted from peat in the Tver area and the sapropel of Lake Seliger behave as complexing sorbents with conditional affinity constants logβ = 3.78 and 3.23 for Cr(III) sorption at HA sites in the peat and sapropel, respectively. In the three-component system Cr(III)-FA-HA, the Cr(III) distribution coefficient between solution and precipitate is controlled by the pH value and FA content in the solution and decreases by 1–1.5 orders of magnitude with increasing fulvic acid content.     

Compositional and source characterization of base progressively extracted humic acids using pyrolytic gas chromatography mass spectrometry

Cyclic base extraction is a commonly used method for the isolation of humic acids from soils and sediments. However, every extract may differ in chemical composition due to the complex nature of humic acids. To better understand the chemical composition of each extract, the heterogeneous property of humic acids and their speciation in environmental samples, eight fractions of humic acids were obtained in the present work by progressive base-extraction of Pahokee peat, and their chemical composition was characterized using two complementary pyrolytic techniques, namely conventional pyrolysis and methylation pyrolysis (TMAH) GC/MS. These quick and effective procedures provide an insight into the structure of macromolecules. The work shows that the lignin-derived aromatic compounds are major components of pyrolysates in both pyrolytic techniques, while aliphatic compounds originating from microorganisms and plants are minor components. Other compounds derived from proteins and carbohydrates at lower concentrations were also detected. Fatty acids were found in the pyrolysis without methylation, indicating their association with humic acid in a free state. These compounds are different from those formed during pyrolysis with in situ methylation, where fatty acids are generally believed to be the cleavage products of carboxylic groups bound to humic acids. A relative decreasing abundance of aromatic components and increasing abundance of aliphatic components in the pyrolysates as the peat was progressively extracted was also observed in this work, suggesting that the extraction of more hydrophobic aliphatics may be delayed in comparison to the aromatic components. Speciation and origin differences may also be important particularly considering that the contribution from lignin organic matter decreased with extraction number, as the contribution of microbial organic matter increased. The observed change in chemical composition with the extracted fractions indicates again that the humic acid distribution and their speciation are complex, and complete extractions are necessary to obtain a representative humic acid sample.     

垃圾渗滤液水溶性有机物对污染土壤中重金属Pb迁移性的影响

采用土柱淋滤试验研究了不同填埋年限的垃圾渗滤液DOM在土壤中垂直迁移及其对土壤重金属Pb淋滤溶出的影响。结果表明,不同填埋年限(0.4~5.12 a)的垃圾渗滤液DOM在土壤中垂直向下的迁移速率存在差异,填埋时间短的垃圾渗滤液DOM在土壤中迁移性较强。与对照相比(不加渗滤液DOM),垃圾渗滤液处理对红壤中土壤重金属Pb的累积解吸率高74.25%;在潮土上高-38.79%,且垃圾填埋年限中期的渗滤液DOM对土壤重金属的溶出影响更显著,说明垃圾渗滤液DOM进入土壤环境对重金属的迁移有促进作用。     

Phosphorus in marine and non-marine humic substances

The phosphorus content of marine humic acids (HA) is in the range of 0.1–0.2%. The C/P ratios of the HA are 300 to 400. Marine fulvic acids (FA) contain 0.4–0.8% P and have C/P ratios of 80 to 100. High molecular weight organic matter dissolved in pore waters (DOM) contains 0.5% P and has C/P of 90. The data suggest that during the formation sequence: Plankton → DOM → FA → HA → Kerogen, phosphorus is lost, mainly in the FA → HA (and possibly also in the HA → Kerogen) step. Diagenesis of sedimentary humic acids is accompanied by loss of phosphorus (as well as of nitrogen) to form HA with C/P ratios of 1000.Soil humic substances resemble marine humates in P content (0.3%) and soil FA's are about three to fivefold enriched in P relative to HA. C/P ratios are lower in soil HA (ca. 200) as compared with marine HA. Humic acids from diagenetic products such as peat and lignite are highly depleted in P. Rough calculations indicate that humate bound P may account for 20–50% of the organic phosphorus reservoir in sediments. The chemical speciation of this P is unknown, but lack of correlation with ash, Fe, Ca or Al content (in marine humates, at least) indicates that it is organically bound.     

Distribution of As,Cr, Ni,Rb, Ti and Zr between peat and its humic fraction along an undisturbed ombrotrophic bog profile (NW Switzerland)

Ombrotrophic bogs are useful records of the impact of historical human activity on heavy metal contamination. Several studies concerning the trace element record (mainly Pb and Hg) in these particular environments have been carried out in recent years, although the role of humic substances has often not been considered. In particular, of the components of peat organic matter, fulvic acids and low molecular weight compounds are generally responsible for the mobility of trace elements through the profile, while humic acids (HAs) are involved in the formation of more stable organo-mineral complexes. In order to study the parallel distribution of As, Cr, Ni, Rb, Ti and Zr in bulk peat and the corresponding HAs, a peat core (10 × 10 × 81 cm) was collected from Etang de la Gruère (Switzerland) and cut into 27 slices of 3 cm. The samples were freeze-dried and milled very finely, and HAs extracted from each sample. Both peat and HAs were analyzed using an energy-dispersive miniprobe X-ray fluorescence multielement analyser (EMMA-XRF). Of the considered elements, Ni showed a great affinity for the humic acid component, while Cr was concentrated mainly into humic material from the deeper layers. On the other hand, Ti, Zr and Rb seemed to reflect the variation in mineral material both in peat and HA samples, while the As content of both materials reflected the environmental conditions characterizing the bog.