水体中溶解有机物的特性与测量

系统评述了水体中溶解有机物的特性及测量方法。介绍了水体中溶解有机物的研究概况,指出了开展水体中溶解有机物定量监测的必要性;详述了水体中溶解有机物的激光诱导荧光测量方法、对水体中有机物荧光光谱进行分析的特征光谱荧光标记技术和荧光强度归一化处理技术,以及利用激光诱导荧光方法测量水体中溶解有机物浓度的标定方法;综述了多种因素对利用激光诱导荧光方法测量的影响。     

用三维荧光谱图分析原水输送过程中藻类和有机物的变化

采用新型分析技术三维荧光谱图方法对深圳东江水源工程水体中藻类进行了荧光分析。实验结果表明,水体中有较丰富的藻类,其中蓝藻、绿藻呈优势藻种,实验期间沿程水体叶绿素a浓度在1.71~16.43μg/L之间,藻密度在72.92万~1 375万个/L之间。三维荧光方法能较好表征水体中生长藻类种类和数量,三维荧光强度F(A.U)与叶绿素a浓度Chla(μg/L)、藻密度N(104个/L)呈较好的线性关系。三维荧光方法能较好的鉴别水体中可溶性有机物腐殖酸和蛋白质,并表征其含量多少。     

洱海沉积物间隙水中溶解有机质的地球化学特性

对洱海沉积物间隙水中溶解有机质(DOM)含量、紫外可见吸收、荧光以及分子量等的垂直分布特征进行了研究。结果表明,DOC含量在沉积物水界面明显富集,随后急剧下降,6cm处达到最小值,随后呈上升趋势。DOC与吸光度值、荧光发射光谱强度之间具有一定的线性相关关系。DOM的E3/E4值范围在1～6之间,绝大多数在1～35之间。表征DOM中腐殖质来源的指标荧光指数值处于148～159之间,说明DOM以陆源输入为主。此外,洱海沉积物间隙水DOM分子量分布呈多峰分布模式,重均分子量(M_w)值在1462～1953Da之间,数均分子量(M_n)值在547～900Da之间,多分散性系数ρ值在202～305之间。随着沉积深度增大,M_w和M_n有略微的增大趋势,但变化不大。沉积物的氧化还原条件、微生物活动以及铁、锰氧化物等在沉积剖面的差异是控制间隙水中DOM各种地球化学特性的主要因素。     

Determination of Hg and MeHg complexation with dissolved organic matter by fluorescence quenching titration

In natural waters inorganic mercury （Hg） and methylmercury （MeHg） are complexed with a variety of inorganic and organic ligands, such as OH^-, Cl^-, sulfide, thiols, and dissolved organic matter （DOM）. The bioavailability and toxicity of Hg and MeHg are related to their speciation, instead of their total concentrations. Among these species, Hg-DOM and MeHg-DOM complexes are the least known, due to the complexity and site-specificity of DOM in natural waters. Here we report the complexation between DOM and Hg or MeHg using fluorescence spectroscopy. The Suwannee River fulvic acid, peat humic acid, amino acid typotophan, and natural organic matter from the Suwannee River, Nordic River, and Delta Marsh were studied at their respective excitation/emission maxima,     

洞穴溶解有机质组分和循环过程的季节变化特征

溶解有机质（DOM）是岩溶碳汇的关键部分和重要的碳源,但是对于DOM在岩溶含水层中的性质和代谢过程的研究仍然有限。本研究以重庆雪玉洞地下河为例,对洞穴有机碳的来源、组成以及微生物作用对季节补给源变化的响应进行探讨,为进一步了解微生物介导的有机碳转化过程提供研究基础。运用三维荧光EEM研究水体有色溶解有机质（CDOM）的性质和组分并反演地下河水中有机质的来源和组成,结合地下河水水化学特征和16S rDNA细菌群落及功能多样性的季节变化特征,以了解季节性补给源的变化对洞穴地下水DOM输入和性质的影响。结果发现,雪玉洞地下河水以微生物内源有机质为主（61%~77%）,降雨是引起岩溶给地下河水中CDOM光谱特征变化的最重要因素,雨季外源有机质输入增加,地下河水中外源有机碳组分含量和芳香性、腐殖酸类物质增加,细菌群落多样性和代谢功能基因随之变化,洞穴中向外输出的外源有机碳增加;旱季地下河水滞留时间和蒸发作用增强,因而微生物对有机质的代谢降解过程更加充分,向洞外输出的有机碳以内源为主。本研究有助于增加对岩溶洞穴地下水系统中微生物对有机碳转化过程的理解。     

Origin and three-dimensional fluorescence spectrum of the chromophoric dissolved organic matter in Yangtze estuary, East China

Dissolved organic matter （DOM） is an important chemical component in natural water. Chromophoric dissolved organic matter （CDOM）, a fraction of optical properties, plays art important role in the biogeochemical cycle of nutrients in aquatic environment. People realized that DOM cycle is crucial in the global carbon and nitrogen flux, and also is inherently related to nutrients and trace metal elements. Therefore, CDOM was concerned by scientists in global oceanography and limnology fields. Water samples were collected from three sections （North Channel, South Channel and Zhuyuan） of the Yangtze （Changjiang River） estuary in March 2006 Three-dimensional excitation emission matrix （3-DEEM） fluorescence spectra were analyzed for those filtrates through Whatman GF/F filters. Dissolved organic carbon （DOC） was also measured by TOC analyzer. The tidal variety was also taken into account. The 3-D EEM fluorescence scans suggested the fluorescence characteristics of humic acid （Ex=332-344 nm, Em=439-451 nm） and fulvic acid （Ex=250-254 nm, Em=472-478 nm） were obvious, and the fluorescence group of protein-like and tyrosine （Ex=230 nm, Em=283 nm） was also found. They are mainly composed of CDOM in the Yangtze estuary. Further data analysis, especially the fluorescence index （f 450/500）, showed that terrestrial signal was rather strong （1.41-1.65） in the surface water, however, some terrestrial CDOM signals of bottom water showed excursions （1.28-1.39）. On the other hand, anthropogenic sign was impressed in the waters of Zhuyuan, which is one of the main drain outlets of Shanghai Metropolis. DOC concentrations ranged from 2.2 mg/L to 3.4 mg/L in Zhuyuan and South Channel, and from 2.0 mg/L to 2.4 mg/L in North Channel. The tide effect played a role in the composition of the CDOM measured by 3-D fluorescence scan technology.     

Optical characteristics and solar photodegradation of dissolved organic matter in Arkansas River, USA

Dissolved organic matter （DOM）, a mixture of numerous organic compounds of 30 to 300000 D, exists in all natural water resources including rivers, lakes and oceans, and plays a very important role in global carbon cycle and ecology. The DOM molecules absorb UV light strongly in short wavelengths and prevent microorganisms from being damaged by solar UV irradiation. Meanwhile, the large DOM molecules are then photodegraded into inorganic carbon and smaller organic molecules which are easier for bacterioplankton to digest. The Arkansas River is one of the largest rivers in the US, and a major input of organic materials to the Mississippi River and Gulf of Mexico. However, the photochemical properties of the DOM in the river water have not been investigated. To study this photodegradation process of the Arkansas River, water samples from the river were collected, filtered, sealed into quartz flasks, and exposed to sunlight for up to 15 hours. Some samples were retrieved from the flasks at certain time intervals. The intensity of the sunlight was measured during the exposure process at 30 min to 1 hr intervals. UV-vis absorption, fluorescence emission, 3D fluorescence spectra and DOM concentrations were determined for all retrieved samples. It was found that the total DOM concentration decreased while the dissolved inorganic carbon （DIC） concentration increased in the samples. UV absorption and fluorescence intensity of DOM decreased exponentially. The disappearance rate of UV absorption varied with wavelength. The loss of integral fluorescence was about 2.6 times that of the UV absorption at the excitation wavelength. In addition, the quantum yields also decreased, and the peak position of 3D fluorescence scan shifted to shorter wavelength.     

骆驼山煤矿不同含水层水中荧光性DOM分布特征

结合骆驼山煤矿不同含水层水文地质条件,通过检测分析各含水层水中天然有机质三维荧光光谱、总有机碳TOC和无机阴离子,研究了荧光性溶解有机物(Dissolved Organic Matter,DOM)的分布特征,结果表明:TOC和有机物在254 mm波长紫外光下的吸光度UV₂₅₄整体上随着含水层层位加深而减少,奥灰水中TOC和UV₂₅₄比其他水体分别低2~3.3倍和2.4~4.7倍;有机物芳香度也逐渐降低,紫外吸光度SUVA值在地表水、第四系水、砂岩水和奥灰水中分别为3.28、2.27、2.24和1.96。地表水和第四系水的三维荧光光谱(3DEEM)图存在5个指纹区域,随着地层层位的加深,水中有机物总体上呈递减趋势,最深层的奥灰水中没有酪氨酸、疏水性有机酸和海洋性腐植酸,而色氨酸的荧光强度比其他水体都高,表明地下水中有机物会反应生成色氨酸类有机物。奥灰水中TOC随着地下水流向逐渐减少(从0.27 mg/L减少至0.22 mg/L);有机物反应生成色氨酸,导致色氨酸FI随着水流而逐渐增加;根据3DEEM光谱图,骆驼山煤矿区奥灰水中有机物比较稳定,能够明显区分出其作为突水水源的特征离子。     

不同地质年代煤矸石中有机质的溶出特征对比

分别以神东矿区补连塔矿侏罗纪煤矸石和保德矿二叠纪煤矸石为研究对象,通过浸泡实验,结合三维荧光光谱测试技术及平行因子分析法,对比研究2种煤矸石中有机质的溶出特征,这对于开展煤矿区地下水库水处理机理研究具有重要意义。研究结果表明：由于煤矸石自身矿物组成不同,补连塔矿煤矸石浸泡液中总离子质量浓度高于保德矿,且2种煤矸石浸泡液均呈弱碱性;其中补连塔矿煤矸石溶解性有机质（DOM）中含有较多的共轭双键或苯环类简单芳香族化合物,以富里酸和分子量较大的陆源类腐殖质为主,且含量普遍高于保德矿,而保德矿煤矸石中富里酸和酪氨酸类有机质较多。根据DOM样品荧光指数（FI）、生物源指数（BIX）、腐殖化指数（HIX）的计算结果,2种煤矸石中DOM主要为内源有机质,并具有较强的自生源特征,且煤矸石形成地质年代越早,煤矸石DOM样品的\     

卤水中溶解性有机质的光谱学性质和光降解行为研究

卤水中溶解性有机质(dissolved organic matter,DOM)会对盐田日晒工艺和产品质量产生不利影响,如盐田卤水的蒸发速率减缓、蒸发度减小以及提取的矿物产品带有刺鼻的气味、浓重的颜色等。因此,对具有资源开发利用价值的卤水体系中DOM结构和性质的研究可以为后续DOM的有效去除或在DOM共存体系中调控无机盐结晶工艺路线提供有效的指导意见。本文以自然界中广泛存在的两种不同类型的卤水体系,即盐湖卤水DOM(SLDOM)和油田卤水DOM(OFDOM)为研究对象,采用溶解性有机碳(dissolved organic carbon,DOC)分析、光谱学分析和平行因子分析等手段对DOM的含量、分子量分布特征、光谱学结构和光降解行为开展了研究。DOC和荧光分析表明SLDOM和OFDOM的DOC含量和生物指数(BIX)值相似;与OFDOM相比,SLDOM的腐质化指数(HIX)值和高分子量组分(HMW)比例偏高;特别吸收光谱(SUVA₂₅₄)和糖类化合物含量检测结果表明,SLDOM和OFDOM的HMW组分中含有的芳香类和糖类化合物所占比例比低分子量组分(LMW)高;三维荧光谱图分析(EEM)结果表明,SLDOM主要以腐殖质类物质为主,而OFDOM以蛋白质类组分为主。此外,DOM的荧光组分在不同分子量中的分布也存在明显差异:对于SLDOM,富里酸主要分布在HMW DOM中,而腐殖酸主要在LMW DOM中;对于OFDOM,芳香胺类蛋白组分主要分布在HMW DOM中,色氨酸和酪氨酸类蛋白组分主要分布在LMM DOM中。在光降解实验中,SLDOM和OFDOM的DOC含量随光照时间增加而逐渐减少,分别下降了29.32%和15.11%。进一步的分析表明,光照过程中两种卤水中糖类化合物均减少,小分子量的DOM优先分解。此外,在光照过程中SLDOM芳香类化合物增加,腐质化程度基本不变;OFDOM芳香类化合物减少,腐质化程度增加。EEM平行因子分析(PARAFAC)结果表明,SLDOM荧光组分在光降解过程中荧光强度增加,而OFDOM荧光强度减少。     

Ultraviolet absorbance titration for the determination of conditional stability constants of Hg（Ⅱ） and dissolved organic matter

Strong interaction between natural dissolved organic matter （DOM） and Hg（Ⅱ） may influence the transport, conversion, toxicity and bio-validity of mercury in the environment. In this paper ultraviolet （UV） absorbance titration was employed for the first time for the determination of the conditional stability constants of Hg（Ⅱ） and （DOM）. With increasing Hg（Ⅱ） concentrations, the UV absorbance of fulvic acid, humic acid, and DOM in river increases progressively. By linear and non-linear model fitting, the conditional stability constants （lgK） of Hg（Ⅱ） and DOM were worked out to be 3.54-4.93 and 3.64-4.85, respectively. The results are consistent with those acquired by the typical fluorescence quenching titration method, with the maximum relative error of lgK being 2.6% and the average relative error being 0.2%. The UV absorbance titration method has the advantages of rapid determination, simple performance, and it will probably become a new approach to studying interactions between DOM and trace metallic ions.     

大气颗粒物中水溶性有机物的理化性质和污染特征研究进展

水溶性有机物(WSOM)是颗粒物的重要组成部分,来源广泛,组成复杂,对大气能见度、全球气候变化以及人体健康均有影响。本文主要综述了近5年国内外有关WSOM的研究成果,主要结论如下:(1)脂肪族化合物是WSOM的主要化学组分,而芳香族化合物含量相对较低;(2)WSOM相对于水溶性无机离子的占比增加时,气溶胶的吸湿增长因子相对较低;(3)不同来源的WSOM,其吸光性能差异较大,生物质燃烧源对WSOM的吸光贡献最大;(4) WSOM主要来自于生物质燃烧和光化学反应的二次生成,其秋、冬季浓度水平明显高于春、夏季,城区和郊区浓度水平均明显高于地区背景点。     

从水体到沉积物:探寻有机质的沉积过程及其意义

自然界中有机质分布广泛、类型多样且性质各异,不论在水体还是在沉积物(岩)中都扮演着重要的角色。因此,探讨各类型有机质聚集和沉积过程的差异性,对深化认识有机质沉积特征和演化规律具有重要的意义。生物体在生长过程中产生了许多有机质,包括生物体自身、生物残体、动物排泄物以及生物分泌的有机分子等,各类型有机质的性质差异极大。由于研究方法的不同,可将海洋中有机质划分为颗粒有机质(particulate organic matter,POM)和溶解有机质(dissolved organic matter,DOM),而DOM又可划分为胶体有机质(colloidal organic matter,COM)和真溶解有机质;从聚合体形式上看,又有海雪和悬浮体等存在形式。进一步分析发现有机质的形态包括生物体、生物残体、排泄物和有机质聚合体等,并且各类型有机质与无机矿物以不同的形式共存。此外,DOM与POM间存在一定的转化关系。这些性质和特征架起了不同类型有机质间聚集和沉积的桥梁。在沉积物(岩)中通过粒度或密度分级分离及孢粉相分析,也发现不同类型的有机质,如生物体、生物残体和无定形等,它们常与特定的无机矿物共生,如无定形多富集在黏粒级颗粒中,而生物体和生物残体多富集在粗颗粒中。进一步溯源发现沉积物(岩)中的各类有机质与生物有机质或海洋中有机质的类型极具相似性,这些特征展现各类型有机质在沉积过程中的差异性。综合有机质的形态、性质以及与矿物共生关系,认为有机质可通过机械沉积、化学沉积和生物沉积等3种不同的方式沉积保存,其中机械沉积的有机质以惰性的生物残体为主,化学沉积的有机质以活性极强的无定形为主,生物沉积有机质以活性较强的微生物和粘附物为主。有机质沉积方式及有机质特征、矿物—有机质间关系和保存条件的差异,决定了有机质的演化命运的不同,进而对有机质生烃以及碳循环产生重要的影响,因而应引起人们的高度关注。     

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…     

Phosphorus features in FT-IR spectra of natural organic matter

Fourier-Transform Infrared （FT-IR） spectroscopy has been used extensively to characterize natural organic matter （NOM）. Absorption bands at 1100-1000 cm^-1 in the FT-IR spectra of NOM have been frequently assigned to alcoholic and polysaccharide C-O stretching or to vibrations of SiO2-related impurities. However, these interpretations do not consider that a strong band associated with P-O bonds of phosphate also appears in the same region. We evaluated the correlation between absorbance in this region and P content of 19 NOM samples from terrestrial, aquatic and plant shoot sources. In the spectra of 10 humic and fulvic acid samples, shoulder to minor bands appeared around 1050 cm^-1. Absorbance intensity at 1050 cm^-1 （Y） was linearly related to P content （X） by the following： Y=4.38X＋0.3 l, with R2=0.90. We did not observe such a close correlation between absorbance and P content in two aquatic NOM samples. Apparently, this is because the aquatic NOM samples were concentrated by reverse osmosis, which would have concentrated not only humic and fulvic acids but also other soluble organic solutes present in natural waters. In the FT-IR spectra of seven dissolved organic matter （DOM） samples obtained from dried plant shoots, broad and/or multiple bands around 1075 cm^-1 were observed with a shoulder at 977 cm^-1. These characteristics were more like those of organic phosphate compounds （such as inositol hexaphosphate）. However, solution 31P nuclear magnetic resonance spectroscopic analysis showed no significant amount of organic phosphate present in these samples.     

夏季丰水期河流输入对太湖有色可溶性有机物的贡献

结合2008年夏季丰水期对太湖上游直湖港、大浦河、长兜港3条河流有色可溶性有机物(CDOM)吸收和三维荧光的测定分析,探讨了夏季丰水期时河流输入对太湖中CDOM的贡献.3条河流中直湖港CDOM浓度最高,大浦河次之,长兜港最低,反映了太湖北部外源河流污染物输入大于西南部.3条河流内CDOM吸收α(355)的均值为(4.7...     

Dissolved organic matter fluorescence spectroscopy as a tool to estimate biological activity in a coastal zone submitted to anthropogenic inputs

Here we report on an investigation of the three-dimensional excitation-emission-matrix (EEM) fluorescence spectra of unconcentrated water samples collected in 1996, 1998 and 1999 at a site particularly propitious for macro-algae development. The degradation of these macro-algae was studied to determine the influence of their exudates on natural water EEM fluorescence spectra. This work demonstrates that biological activity is one of the major factors involved in the formation of the blue-shifted fluorescence band observed in marine waters (β component Ex/Em=310–320 nm/380–410 nm); our study also shows that fluorescence can be used to evaluate the biological activity both quantitatively and to determine its different phases.     

有机质含量对淤泥固化效果影响的试验研究

淤泥固化技术是淤泥资源化利用的一个重要方法,而有机质对淤泥固化效果的影响是淤泥固化技术研究中的重要课题。在淤泥固化的试验研究中发现有机质含量对淤泥固化的效果有着显著影响。通过对不同有机物含量的固化试验揭示了该种影响的规律,发现淤泥中的有机质存在着一个极限含量4.3 %,当超过这一极限含量后,有机质量的增加不再对固化效果产生更大的影响。根据这一研究结果,提出了对于高有机质淤泥采用水泥-石膏进行固化的方法。     

Fractionation of dissolved organic matter affected by polyvalent metal cations

The purpose of the study was to evaluate the influence of polyvalent cations known to form complexes with natural organic substances on the operational fractionation of dissolved organic matter (DOM) using XAD-8 adsorber resin. Dissolved organic matter solutions from a forest floor were treated with increasing concentrations of polyvalent metal cations (Ca²⁺, Al³⁺, Fe³⁺) at different pH levels. Then the concentrations of total dissolved organic carbon (DOC) and the distribution between hydrophilic and hydrophobic DOC were determined. The concentrations of total DOC decreased slightly when the C/metal ratio was less than 10, especially for Al and Fe. Hydrophilic DOC increased and hydrophobic DOC decreased with increasing concentrations of metal cations. Effects increased in the order Ca<Al<Fe and were more pronounced at low DOC concentrations and high pH values. The reason for the reduction of the DOC concentrations seemed to be the formation of insoluble metal–DOM complexes, while soluble metal–DOM complexes may induce an alteration of the distribution between hydrophilic and hydrophobic DOC. Thus, the polyvalent cations and their concentration need to be considered when DOM fraction distributions, determined with XAD-8 resin, of different waters are compared, especially at low DOC contents and high pH.     

Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.