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1.
This study examined the dissolved organic matter (DOM) components of cow dung using a combination of fluorescence (excitation–emission matrix, EEM) spectroscopy and parallel factor (PARAFAC) modelling along with eleven trace metals using ICP-MS and nutrients (NH4+ and NO3?) using an AA3 auto analyser. EEM–PARAFAC analysis demonstrated that cow dung predominantly contained only one fluorescent DOM component with two fluorescence peaks (Ex/Em = 275/311 nm and Ex/Em = 220/311 nm), which could be denoted as tyrosine by comparison with its standard. Occurrence of tyrosine can be further confirmed by the FTIR spectra. Trace metals analysis revealed that Na, K and Mg were significantly higher than Ca, Fe, Mn, Zn Sr, Cu, Ni and Co. The NH4+ concentrations were substantially higher than NO3?. These results thus indicate that the dissolved components of the cow dung could be useful for better understanding its future uses in various important purposes.  相似文献   

2.
The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.  相似文献   

3.
鲁宗杰  邓娅敏  杜尧  沈帅  马腾 《地球科学》2017,42(5):771-782
水体中溶解性有机质(dissolved organic matter, DOM)是含水层中砷释放的主控因素之一.江汉平原河湖众多、沟渠广布,地表水体与浅层地下水的交互作用使得DOM的组分特征及其强度有显著差异.为查明江汉平原地下水中溶解性有机质在砷迁移转化过程中的作用,对江汉平原地表水和浅层地下水进行三维荧光光谱分析,使用平行因子分析法提取水体中有机质的分子组成、功能特点和荧光特征,并分析各组分相对含量与地下水中砷与铁的关联.江汉平原水体中DOM包括3种主要组分,组分C1、C2为类腐殖质,C2是生物降解过程中产生的小分子,C3为类蛋白物质.地下水DOM以类腐殖质组分C1、C2为主,地表水以类蛋白类物质C3和小分子腐殖质C2为主.高砷地下水中DOM以陆源为主,主要通过两种途径促进As的迁移转化:(1) DOM的腐殖质组分充当微生物群落的电子运输工具,促进微生物作用下的有机质氧化和铁氧化物的还原,并伴随As的释放及大量溶解性有机碳(dissolved organic carbon, DOC)和HCO3-的产生;(2) As以铁等金属阳离子为桥接物与腐殖质结合,通过形成As-Fe-DOM络合物,导致地下水中砷的迁移.   相似文献   

4.
Properties of fluorescent dissolved organic matter in the Gironde Estuary   总被引：5，自引：0，他引：5  
The isolation, characterization and study of the properties of aquatic dissolved organic matter (DOM) still represent a challenge because of the heterogeneity, complexity and low concentration of organic material in natural waters. Based on its ability to interact with contaminants and thus to modify their transport and bioavailability, DOM is of interest for environmental purposes. The objective of this work was to better characterize DOM in the Gironde Estuary (southwestern France). The estuary represents an exchange zone between the continent and the Atlantic Ocean and conditions the transfer of organic and inorganic substances from the continental to the oceanic environment. Several samples were collected along the estuary during three cruises in 2002 and 2006. They were analysed using excitation–emission matrix (EEM) spectroscopy, a sensitive technique that allows direct analysis of water samples. Fluorescent DOM and dissolved organic carbon (DOC) did not behave conservatively in this estuarine system, i.e. the organic material did not undergo simple dilution from the upstream to the downstream part of the estuary. A seasonal variability in DOC content was pointed out, whereas few seasonal variations in DOM fluorescence were observed. DOM sources and processing in the estuary were further evaluated by determining two fluorescence indices – the humification index (HIX) and the index of recent autochthonous contribution (BIX). By applying these indices, the relative degree of humification (HIX) and autotrophic productivity (BIX) could be assessed. Based on the fluorescence and DOC results, the estuary was divided into three zones depending on salinity (S) and characterized by specific DOM: (i) A turbid zone of low salinity (S < 5) and high suspended particulate matter concentration with increase in the intensities of the α′ and α fluorophores, characteristic of humic-like compounds. (ii) A mid-estuarine zone (5 < S < 25) characterized by low autotrophic productivity and containing strongly degraded organic material, as shown by the low values of BIX and high values of HIX. (iii) A higher salinity area (S > 25) characterized by increased autotrophic productivity and a marked marine influence, and associated with high and low values of BIX and HIX, respectively. The HIX and BIX indices were shown as useful tools for readily defining and classifying DOM characteristics in estuarine waters.  相似文献   

5.
The fluorescence properties of groundwaters from sites in two UK aquifers, the Penrith Sandstone of Cumbria and the Sherwood Sandstone of South Yorkshire, were investigated using excitation–emission matrix (EEM) fluorescence spectroscopy. Both aquifers are regionally important sources of public supply water and are locally impacted by pollution. The Penrith Sandstone site is in a rural setting while the Sherwood Sandstone site is in suburban Doncaster. Fluorescence analysis of samples from discrete sample depths in the Penrith Sandstone shows decreasing fulvic-like intensities with depth and also shows a good correlation with CFC-12, an anthropogenic groundwater tracer. Tryptophan-like fluorescence centres in the depth profile may also provide evidence of rapid routing of relatively recent applications of organic slurry along fractures. Fluorescence analysis of groundwater sampled from multi-level piezometers installed within the Sherwood Sandstone aquifer also shows regions of tryptophan-like and relatively higher fulvic-like signatures. The fluorescence intensity profile in the piezometers shows tryptophan-like peaks at depths in excess of 50 m and mirrors the pattern exhibited by microbial species and CFCs highlighting the deep and rapid penetration of modern recharge due to rapid fracture flow. Fluorescence analysis has allowed the rapid assessment of different types and relative abundances of dissolved organic matter (DOM), and the fingerprinting of different sources of organic C within the groundwater system. The tryptophan:fulvic ratios found in the Penrith Sandstone were found to be between 0.5 and 3.0 and are characteristic of ratios from sheep waste sources. The Sherwood Sandstone has the lowest ratios (0.2–0.4) indicating a different source of DOM, most likely a mixture of terrestrial and microbial sources, although there is little evidence of pollution from leaking urban sewage systems. Results from these two studies suggest that intrinsic fluorescence may be used as a proxy for, or complementary tool to, other groundwater investigation methods in helping provide a conceptual model of groundwater flow and identifying different sources of DOM within the groundwater system.  相似文献   

6.
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。  相似文献   

7.
Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion concentrations (Cd, Cu and Zn) in water samples collected from the epilimnion of 14 lakes in the Rouyn-Noranda area (600 km north-west of Montreal, QC, Canada). Lakes were selected to represent a wide range of physico-chemical characteristics (hardness, pH, dissolved organic matter—DOM, degree of metal contamination), to determine the influence of these parameters on metal speciation. Total dissolved metal concentrations, as determined within the diffusion cells, varied over one to two orders of magnitude: [Cd] 0.19–2.9 nM; [Cu] 36–190 nM; [Zn] 7–2,800 nM. The proportion of total dissolved metal present as free Cd2+ and Zn2+ was relatively constant for the 14 selected lakes, despite the wide pH (4.5–8) and DOM (3–23 mg C/L) ranges, probably reflecting the inverse relationship observed between pH and DOM; this proportion did, however, vary with DOM and pH for Cu. Our experimental free metal ion concentrations were compared with those calculated with the thermodynamic models WHAM (Windermere Humic Aqueous Model VI) and ECOSAT 4.7 (incorporating the NICA-Donnan model). Measured and calculated values were in reasonable agreement for both Cd and Zn although measured values were generally slightly higher, i.e. less than one order of magnitude. For several lakes, measured free Cu concentrations were, however, much higher than the calculated values, suggesting that these models overestimate Cu complexation. The gap between measured and calculated free metal ion concentration becomes more important as the total metal concentration decreases and as pH increases.  相似文献   

8.
The patterns of dissolved organic matter (DOM) fluorescence properties were examined in a Precambrian shield stream over a seven-month field study. Unique spatial and temporal patterns of simultaneous changes were observed in dissolved organic carbon concentration (DOC), humic-like fluorescence intensity, maximum excitation and emission wavelengths and fluorescence index (the ratio of the emission intensity at a wavelength of 450 nm to that at 500 nm at an excitation wavelength of 370 nm). The spatial change indicates the alteration of DOM along the length of the stream, and temporal change corresponded to a drought event in August. In contrast to humic-like fluorescence, the protein-like fluorescence shows considerable variability, suggesting its ephemeral nature. There were strong relationships between humic-like fluorescence intensity, fluorescence index, maximum Ex/Em wavelengths, DOC concentration and molecular size of DOM. This study has significant implications to the understanding of the nature and biogeochemical cycling of DOM.  相似文献   

9.
《Geochimica et cosmochimica acta》1999,63(19-20):3311-3319
Copper speciation was determined monthly at seven sites on four rivers in southern New England to understand which geochemical factors control free metal ion concentrations in river water. Samples were conventionally filtered (<0.45 μm) and then ultrafiltered (3.000 molecular weight cut-off) to determine Cu speciation in the truly dissolved size fraction. Differential pulse anodic stripping voltammetry (DPASV) was used to quantify natural organic complexation and cathodic stripping square wave voltammetry (CSSWV) to measure directly both Cu sulfide complexes and total EDTA concentrations. The results showed both dissolved organic matter (DOM) and sulfide complexation dominate Cu speciation and control the concentrations of free ion. Free Cu2+ was calculated to be in the subnanomolar range for the majority of the year. Only in the winter months, when concentrations of DOM and metal sulfides complexes were at a minimum were free metal ions directly measurable by DPASV at low nanomolar concentrations. The extent of sulfide complexation appears to be dominated by the size of headwater marshes (upstream sampling sites) and by the amount of sewage treatment plant effluent (downstream sites). DOM complexation was related to the organic matter composition and followed model organic ligands. Indirect evidence suggests variations in river water pH and Ca2+ (metal competition) has only a minor role in Cu complexation. Measured concentrations of total EDTA suggest this synthetic ligand can control Cu speciation in some highly developed watersheds; however, competition from Ni (and possibly Fe) limits the extent of this complexation.  相似文献   

10.
To elucidate the influence of tidal marshes on the amount and chemical structure of chromophoric dissolved organic matter (CDOM) in adjacent coastal waters, surface water samples were collected along three cross-marsh transects in tidal marshes within the Changjiang Estuary. In addition, three sediment cores were collected from the marshes and incubated for 10 h in the laboratory after adding overlying tidal waters. Nutrients, DOC, absorption, fluorescence excitation–emission matrix (EEM) spectroscopy, and other parameters were measured in these samples, which clearly illustrated releases by the tidal marshes of DOC, and CDOM absorbent and fluorescent molecules. To characterize the chemical nature of the marsh-derived CDOM, variations in a suite of optical indices (including molar absorptivity, absorption spectral slope, fluorescence quantum yield, and fluorescence ratios between certain excitation/emission locations) in these samples were plotted against the offshore distance of the stations as well as the incubation time. From the literature, it has been suggested that these variations are closely associated with molecular weight, aromaticity, and humic/fulvic or allochthonous/autochthonous ratios in the CDOM mixtures. This study showed that the CDOM fluorophores changed to more humic-like and were less protein-like from sea to land across the marsh gradients. Furthermore, subtractions between EEM spectra before and after laboratory incubations were applied to illustrate in greater detail the properties of the pure fluorescent compounds exchanged at the sediment–overlying water interface.  相似文献   

11.
Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.  相似文献   

12.
Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O2 exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.  相似文献   

13.
为了解包气带土壤DOM组成特征, 探索其对砷向地下水中迁移的影响, 对江汉平原高砷区土壤DOM进行了三维荧光光谱分析.结果表明DOM主要为类腐殖质成分, 芳香性官能团的减少导致荧光强度随包气带深度增加而变小, 局部深度荧光信号不规则变化指示非均质土壤剖面上DOM组分或主导官能团的变化.平行因子分析表明, DOM组分可更细致地分解为4种组分, 与微生物源的还原、氧化醌类和陆生的腐殖质富里酸类等相似.砷很可能在DOM腐殖质成分络合作用下与之随水体一起向下迁移, 砷的迁移也可能与微生物源的醌类作用过程有关.三维荧光光谱分析准确、快速地刻画了包气带土壤DOM的组分类别及空间变化特征, 初步揭示了DOM影响砷迁移的可能作用方式, 为进一步的地下水砷污染机制的研究提供了重要的参考信息.   相似文献   

14.
The contents of different organic matter components and dissolved organic matter (DOM) release kinetics of the sediments from the middle and lower reaches of the Yangtze River region were investigated, and their relationships discussed. The results show that organic C (OC) ranged from 8.14 to 43.65 g kg−1, dissolved organic C (DOC) from 0.38 to 1.38 g kg−1, active organic C (AOC) from 1.12 to 4.45 g kg−1, heavy fraction organic C (HFOC) from 6.86 to 39.08 g kg−1, accounting for 2.42-9.34%, 8.66-29.72% and 84.29-93.18% of OC, respectively. With increasing of OC content the ratios of DOC to OC and AOC to OC decreased. The contents of AOC, DOC, light fraction organic C (LFOC) and their contribution ratios to OC in studied sediments were higher than those reported in soils. The DOM release process of the studied sediments includes rapid and slow stages, and the rapid release occurred within 30 min, mainly in 5 min. The DOM release kinetic data in this investigation can be best fitted by the Power Function model. The correlations between total N (TN), total P (TP), OC, DOC, AOC, LFOC, HFOC and the DOM release kinetic parameters (k, c, a, b, rate30) of the sediments were significant. There were also significant correlations between TN, TP, OC, DOC, LFOC and HFOC in sediments. So the DOM release from sediment was not only related to the OC content, but also related to the organic matter composition characteristics, especially the contents of DOC, AOC and LFOC.  相似文献   

15.
Information about the chemical electron accepting capacity (EAC) of dissolved organic matter (DOM) is scarce owing to a lack of applicable methods. We quantified the electron transfer from metallic Zn to natural DOM in batch experiments at DOC concentrations of 10–100 mg-C L− 1 and related it to spectroscopic information obtained from UV-, synchronous fluorescence, and FTIR- spectroscopy. The electron donating capacity of DOM and pre-reduced DOM was investigated using Fe(CN)63− as electron acceptor. Presence of DOM resulted in release of dissolved Zn, consumption of protons, and slower release of hydrogen compared to reaction of metallic Zn with water at pH 6.5. Comparison with reaction stoichiometry confirmed that DOM accepted electrons from metallic Zn. The release of dissolved Zn was dependent on pH, DOC concentration, ionic strength, and organic matter properties. The reaction appeared to be completed within about 24 h and was characterized by pseudo first order kinetics with rate constants of 0.5 to 0.8 h− 1. EAC per mass unit of carbon ranged from 0.22 mmol g− 1 C to 12.6 mmol g− 1 C. Depending on the DOM, a calculated 28–127% of the electrons transferred from metallic Zn to DOM could be subsequently donated to Fe(CN)63−. EAC decreased with DOC concentration, and increased with aromaticity, carboxyl, and phenolic content of the DOM. The results indicate that an operationally defined EAC of natural DOM can be quantified by reaction with metallic Zn and that DOM properties control the electron transfer. Shortcomings of the method are the coagulation and precipitation of DOM during the experiment and the production of hydrogen and dissolved Zn by reaction of metallic Zn with water, which may influence the determined EAC.  相似文献   

16.
Arctic landscapes are believed to be highly sensitive to climate change and accelerated disturbance of permafrost is expected to significantly impact the rate of carbon cycling. While half the global soil organic matter (SOM) is estimated to reside in Arctic soils, projected warmer temperatures and permafrost disturbance will release much of this SOM into waterways in the form of dissolved organic matter (DOM). The spring thaw and subsequent flushing of soils releases the highest contributions of DOM annually but has historically been undersampled due to the difficulties of sampling during this period. In this study, passive samplers were placed throughout paired High Arctic watersheds during the duration of the 2008 spring flush in Nunavut, Canada. The watersheds are very similar with the exception of widespread active layer detachments (ALDs) that occurred within one of the catchments during a period of elevated temperatures in the summer of 2007. DOM samples were analyzed for structural and spectral characteristics via nuclear magnetic resonance (NMR) and fluorescence spectroscopy as well as vulnerability to degradation with simulated solar exposure. Lignin-derived phenols were further assessed utilizing copper(II) oxide (CuO) oxidation and gas chromatography/mass spectrometry (GC/MS). The samples were found to have very low dissolved lignin phenol content (∼0.07% of DOC) and appear to originate from primarily non-woody angiosperm vegetation. The acid/aldehyde ratios for dissolved vanillyl phenols were found to be high (up to 3.6), indicating the presence of highly oxidized lignin. Differences between DOM released from the ALD vs. the undisturbed watershed suggest that these shallow detachment slides have significantly impacted the quality of Arctic DOM. Although material released from the disturbed catchment was found to be highly oxidized, DOM in the lake into which this catchment drained had chemical characteristics indicating high contributions from microbial and/or primary productivity. The resulting pool of dissolved carbon within the lake appears to be more biologically- and photochemically-labile than material from the undisturbed system. These disturbances may have implications for projected climate warming; sustained elevated temperatures would likely perpetuate widespread ALDs and further affect carbon cycling in this environment.  相似文献   

17.
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。  相似文献   

18.
近岸沉积物再悬浮期间所释放溶解有机物的荧光特征   总被引：9，自引：0，他引：9  
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.  相似文献   

19.
A major obstacle for characterizing dissolved organic matter (DOM) with ultrahigh resolution mass spectrometry has been its low concentrations in natural waters. Many previous mass spectrometric studies of both terrestrial and marine DOM typically have isolated and concentrated the DOM using solid phase C18 extraction disks, ultrafiltration, or XAD resins, all of which are known to discriminate against many different classes of compounds. We have, for the first time, developed an approach to directly analyze natural water samples with less than 6 mg/l DOC (dissolved organic carbon), using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). We demonstrate the sensitivity and ability of sequential selective ion accumulation (SSIA) to detect the thousands of components in a single freshwater DOM sample without any significant pretreatment. By utilizing SSIA, the baseline noise decreases while signal to noise ratios of the peaks increase, allowing for approximately 40% more formulas to be assigned to peaks in the mass spectra.  相似文献   

20.
The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSIferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSIferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.  相似文献   

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