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1.
Dissolved organic matter (DOM) in sediment pore water is a complex molecular mixture reflecting various sources and biogeochemical processes. In order to constrain those sources and processes, molecular variations of pore water DOM in surface sediments from the NW Iberian shelf were analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and compared to river and marine water column DOM. Weighted average molecular element ratios of oxygen to carbon ((O/C)wa) and hydrogen to carbon ((H/C)wa) provided general information about DOM sources. DOM in local rivers was more oxygenated ((O/C)wa 0.52) and contained less hydrogen ((H/C)wa 1.15) than marine pore water DOM (mean (O/C)wa 0.50, mean (H/C)wa 1.26). The relative abundance of specific compound groups, such as highly oxygenated aromatic compounds or nitrogen-bearing compounds with low H/C ratios, correspond to a high concentration of lignin phenols (160 μg/g sediment dry weight) and a high TOC/TN ratio (13.3) in the sedimentary organic matter and were therefore assigned to terrestrial sources. The lower degree of unsaturation and a higher relative abundance of nitrogen-bearing compounds in the pore water DOM reflected microbial activity within the sediment. One sampling site on the shelf with a high sediment accumulation, and a humic-rich river sample showed a wide range of sulfur compounds in the DOM, accompanied by a higher abundance of lipid biomarkers for sulfate-reducing bacteria, probably indicating early diagenetic sulfurization of organic matter.  相似文献   

2.
A multi-method approach was applied to study changes in dissolved organic matter (DOM) at three estuarine sites with varying salinity, as well as changes resulting from experimental photodegradation. Following measurement of ultraviolet and visible absorption spectra of bulk samples, DOM was isolated using C18 solid phase extraction. The extract was characterized using high performance size exclusion chromatography (HP-SEC) and molecular level characterization was conducted via direct temperature-resolved mass spectrometry (DT-MS) and electrospray ionization mass spectrometry (ESI-MS). The molecular weight distribution of DOM as determined from HP-SEC and ESI-MS varied between techniques, but generally decreased down estuary and with photodegradation for both approaches. Relative differences in molecular weight were significantly correlated with the ratio of absorption coefficients at 254/365 nm. Additionally, photobleaching was significantly correlated with mass spectral characteristics from both DT-MS and ESI-MS. Principal component analysis of DT-MS spectra showed that photoexposure removed different mass spectral characteristics depending on sampling site; however, upon photodegradation, the mass spectral characteristics of both marine DOM and terrestrially dominated DOM approached a common spectrum. We interpret this spectrum, characterized by fragments from aromatic and carbohydrate-like precursors, as photochemically refractory DOM. Our results show that multiple approaches that characterize different aspects of DOM can provide complementary information about its sources and transformation. More specifically, photobleaching results in decreased light absorbance, decreased molecular weight and shifts in the relative abundance of classes of compounds (and broad shifts in m/z values); moreover, these transformations result in photodegraded samples from a low-salinity site which are compositionally similar to samples collected from a mid-salinity site further downstream.  相似文献   

3.
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   

4.
5.
Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO2) and m/z 18 (H2O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ13C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.  相似文献   

6.
选取南海北部下陆坡-深海平原过渡带典型沉积柱状样,通过对其沉积有机质的整体有机地球化学特征进行表征,探讨了南海下陆坡-深海平原区沉积有机质在冰期/间冰期旋回中的赋存状态、来源变化以及与古气候环境之间的相应关系。结果表明,总有机碳(TOC)、总氮(TN)和有机质稳定碳同位素(δ13Corg)与冰期/间冰期旋回有明显的对应关系,冰期时对应高值,间冰期时对应低值;而有机质稳定氮同位素(δ15N)表现为全新世时其值偏低,末次冰消期其值偏高,与气候旋回没有相关性; C/N值和δ13Corg值都表明南海北部下陆坡沉积有机质来源是陆相和海相的混源,且在末次冰期/间冰期尺度上主要以海相来源为主。  相似文献   

7.
The dominant phosphorus compound classes were characterized in marine samples using a new, high recovery method for isolating and concentrating bulk dissolved organic matter (DOM) called combined electrodialysis + reverse osmosis (ED/RO). In contrast to earlier studies that use ultrafiltration (UF) to recover only the high molecular weight DOM, ED/RO is capable of isolating both low molecular weight (LMW) and high molecular weight (HMW) DOM. Samples were collected from a broad range of marine environments: along a transect incorporating coastal and offshore waters off the Southeastern United States, in Effingham Inlet, a Pacific fjord located on Vancouver Island, British Columbia and in the Amundsen Sea, Antarctica. Results from phosphorus nuclear magnetic resonance (31P NMR) analysis reveal a similar abundance of P compound classes among samples, phosphate esters (80–85%), phosphonates (5–10%) and polyphosphates (8–13%). These samples contain significantly higher proportions of polyphosphate P and P esters and lower proportions of phosphonates than measured in previous studies using the UF method. The much higher levels of polyphosphate detected in our samples suggests that polyphosphate is present mainly in the LMW dissolved matter fraction. Polyphosphates in dissolved matter may be present as (or derived from) dissolved nucleotides or organismal polyphosphate bodies, or both. Low molecular weight P esters are possibly composed of phosphoamino acids and small carbohydrates, like simple sugar phosphates and/or dissolved nucleotides. Phosphonates in DOM are more prevalent as HMW phosphonate compounds, which suggests that LMW phosphonates are more readily utilized in marine ecosystems. Overall, the investigation of DOM across a size spectrum that includes both the HMW and the LMW fractions reveals a new picture of phosphorus distribution, cycling and bioavailability.  相似文献   

8.
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   

9.
文章在AMS~14C定年的基础上建立了南海北部MD05-2905钻孔(20°08.17′N,117°21.61′E)末次冰期以来有机地球化学记录的时间序列,利用其中的正构烷烃、甾醇和烯酮等有机分子标志物对南海北坡25ka以来沉积物物源、气候环境变化进行探讨。长链正构烷烃总含量和浮游植物标志物总含量表明25.0~14.5kaB.P.时段南海北部沉积物中陆源物质输入、海洋初级生产力浮游植物输入均较高,14.5~8.5kaB.P.时段迅速降低,全新世8.5kaB.P.之后稳定在较低水平。末次冰期海平面低,陆架出露面积大,陆源物质搬运至沉积地点的距离短,强盛的冬季风及其驱动的洋流有利于大量的陆源物质搬运至该沉积地点;14.5kaB.P.,对应于MWPIa时期,陆源物质输入迅速减少,海洋初级生产力的迅速降低,印证了此时海平面的快速上升。C31/C17物源参数表明陆源物质输入和海洋内生源输入在25.0~14.5kaB.P.时段和14.5~8.5kaB.P.时段分别占据了主要地位,这表明海平面变化对陆源物质输入影响可能更大;全新世8.5ka之后,陆源、海洋内生源输入交替占据主要地位,这可能与东亚季风增强有关。从有机分子标志物研究来看,海平面的变化对陆源物质输入及总海洋初级生产力可能均有重要控制作用,但海洋初级生产力中某些藻类如硅藻可能受控于不同的气候因素。C28甾醇含量指示硅藻在MWPIa和MWPIb时期大量增多,这可能是14.5~8.5kaB.P.海洋内生源输入相对较多的重要原因,同时,对11.0~8.5kaB.P.时段的碳酸钙低值事件可能有一定贡献,但其对海陆环境的响应还有待于进一步研究。  相似文献   

10.
The Pichavaram mangrove ecosystem is located between the Vellar and Coleroon Estuaries in south-eastern India. To document the spatial-depth-based variabilities in organic matter (OM) input and cycling, five sediment cores were collected. A comparative study was carried out of grain-size composition, pore water salinity, dissolved organic C (DOC), loss-on-ignition (LOI), elemental ratios (C/N and H/C), pigments (Chl a, Chl b, and total carotenoids), and humification indices. Sand is the major fraction in these cores ranging from 60% to 99% followed by silt and clay; cores from the estuarine margin have high sand content. In mangrove forests, pore-water DOC concentrations are high (32 ± 14 mg L−1), whereas salinity levels are low (50 ± 5.5‰). Likewise, LOI, organic C and N, and pigment concentrations are high in mangroves. OM is mainly derived from upstream terrestrial matter and/or mangrove litter, and marine OM. The humification indices do not vary significantly with depth because of rapid OM turnover. The bulk parameters indicate that the Vellar and Coleroon Estuaries are more affected by anthropogenic processes than mangrove forests. Finally, greater variability and sometimes lack of specific trends in bulk parameters implies that the 2004 tsunami caused extensive mixing in sediments.  相似文献   

11.
重点探讨了南黄海柱状沉积物中烃类化合物的分子组成特征及其对沉积环境的指示意义,结果显示,沉积柱中总有机碳(TOC)和总氮(TN)具有较好的正相关性,无机氮的影响较弱,这可能跟本区受径流输入的陆源物质的影响较弱有关。上层样品(0~10 cm)中长链正构烷烃占优势,奇偶优势显著,反映了陆源高等植物贡献;藿烷、甾烷的组成则显示该段样品中有机质具有较高的热成熟度;且姥鲛烷(Pr)/植烷(Ph)比值大于1.0,指示沉积环境以氧化为主,这相对不利于海洋源有机质的保存,从而凸显了陆源有机质的贡献。在10~20 cm之间,沉积环境由相对偏氧化向偏还原过渡;20 cm以下表现为强还原性的沉积环境,有机质成熟度较低。中、下层样品中正构烷烃多呈现双峰分布,短链烷烃具有一定的偶奇优势,这可能主要跟海洋浮游生物、藻类及微生物的贡献有关。与渤海烃类化合物的沉积记录进行对比,发现渤海沉积柱中烃类化合物主要跟历史时期不同来源物质的输入及人类活动的影响有关,而南黄海沉积柱中烃类化合物的特征则主要反映了沉积环境和微生物作用对有机质的埋藏保存有重要影响。  相似文献   

12.
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   

13.
Organic acids were released from marine sediments by acid hydrolysis. Ion-exchange chromatography and GC-MS were used to separate and identify the acids. The major compounds detected were galacturonic, glucuronic, mannuronic, 4-O-methylglucuronic, cellobiouronic, guluronic, glyceric, glycolic, lactic and erythronic acids. Numerous biouronic (sugar-uronic acid compounds) and aldonic acids were also found. The low abundance of uronic acids characteristic of terrigenous plants and the similarity of the biouronic composition to that of marine algae indicate a marine algal source for the acids in the sediment. Results from the Black Sea are compared with those from the Baltic Sea and several diagenetic transformations are discussed.  相似文献   

14.
The lateral variability of main geochemical parameters of dispersed organic matter (DOM) in the bottoms sediments of the Ob Bay was studied using materials of areal geological survey. It was found that they correspond to background compositions of estuarine-delta facies of the Western Arctic shelf, being mainly determined by the influx of river run-off and coastal abrasion. The distribution of DOM and its components is controlled by the hydrodynamic regime of the water area and grain-size composition of sediments. The molecular composition of hydrocarbon markers (n-alkanes, cyclanes, and arenes) confirms the dominant role of terrigenous humic material in the formation of DOM of the bottom sediments, while temporal stability of quantitative and qualitative geochemical characteristics indicates the stability of the Ob Bay ecosystem.  相似文献   

15.
洱海沉积物孔隙水中溶解有机质的三维荧光光谱特征   总被引:17,自引:0,他引:17  
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。  相似文献   

16.
通过对南海西部上升流区MD05-2899孔开展高分辨率碳酸盐地层学和XRF岩芯扫描元素地球化学分析,重建了晚第四纪54万来以来东亚夏季风的演化历史,探讨海平面升降对南海西部陆源碎屑供应量的影响。研究选用了ln(Ba/Al)作为该海区古生产力的指标,ln(Br/Al)作为有机物的指标,ln(Ti/Al)作为陆源碎屑供应量的指标。研究结果显示,东亚夏季风在过去54万年以来强度不断增强,具有明显的冰期—间冰期旋回特征,在间冰期强盛和冰期减弱,是控制该海区有机物含量变化的主要因素。东亚夏季风不断强盛可能直接导致了南海周边陆地降雨增强,河流径流量加大,使得南海西部上升流区域的陆源碎屑供应量在间冰期明显高于冰期。研究发现,当相对海平面低于-60 m的时候,大面积暴露的巽他陆架可能向南海西部深水区输入大量陆源碎屑物质,造成研究站位的陆源碎屑供应量在冰盛期出现高值。因此,晚第四纪的东亚夏季风演化和海平面升降共同控制了南海西部上升流区陆源碎屑物质供应量的变化。  相似文献   

17.
To assess heavy metals in mangrove swamps of Sehat and Tarut coastal areas along the Arabian Gulf, 18 sediment samples were collected for Al, V, Cr, Mn, Cu, Zn, Cd, Pb, Hg, Sr, As, Fe, Co, and Ni analysis. The results indicated that the distribution of some metals was largely controlled by anthropogenic inputs, while others were of terrigenous origin and most strongly associated with distribution of aluminum and total organic carbon in sediments. Mangrove sediments were extremely severe enriched with Sr (EF?=?67.59) and very severe enriched with V, Hg, Cd, Cu, As (EF?=?44.28, 37.45, 35.77, 25.97, and 11.53, respectively). Average values of Sr, V, Hg, Cd, Cu, Ni, As, and Cr were mostly higher than the ones recorded from the Mediterranean Sea, the Red Sea, the Gulf of Aqaba, the Caspian Sea, the Arabian and Oman gulfs, coast of Tanzania, sediment quality guidelines, and the background shale and the earth crust. Landfilling due to coastal infrastructure development around mangrove forests, oil spills and petrochemical and desalination effluents from Al-Jubail industrial city to the north were the anthropogenic activities that further enhanced heavy metals in the studied mangrove sediments.  相似文献   

18.
Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography–isotopic ratio–mass spectrometry (GC–IRMS). GC–IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ13C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC–IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.  相似文献   

19.
Major (Al, Ca, Fe, Mg, Mn, Si) and minor (Cd, Pb, Zn) elements of aeolian dust samples collected onboard ship around Italy were analysed, and the concentrations of metal in the dusts were in good agreement with previously published data from the Mediterranean Sea.
The elemental composition of dust samples collected in four subareas (Adriatic, Ionian, Tyrrhenian, and Sicily Channel) was compared with the composition of marine deep sediments obtained in the same regions: Mn, Al, Cd and Zn contents differentiated between the four areas in both sets of samples, suggesting a possible 'geochemical signature' of the atmospheric crustal contribution in marine deep sediments.
An estimate of the relative contribution of atmospheric dry deposition of Cd, Pb and Zn and riverine discharge indicates that: (a) the metals deposited from the atmosphere to the Adriatic basin are a small fraction (2–5%) of those discharged by the Po and Adige rivers; (b) almost the same amounts of Cd, Pb and Zn are delivered to the Tyrrhenian Sea by the atmosphere and by the Arno and Tiber Rivers.  相似文献   

20.
The distributions of methane and hydrocarbons (HC) C2+ throughout the vertical section of the water mass and sediments of the Kara Sea and the estuaries of the Ob and Yenisei rivers were examine during expeditions aboard the R/V “Akademik Boris Petrov” in 1997–2002. Data obtained during the expeditions and extensive information provided by the complex study of the carbon cycle in the aquatic area were used to analyze the genesis of hydrocarbon gases in marine water. The example of particulate matter was used to demonstrate that hydrocarbon gases of the composition C2–C5 contained in seawater are genetically related to aquatic organic matter (OM), regardless of seawater salinity. The hydrocarbon complex is dominated (80%) by higher C4–C5 homologues. The concentration of C4–C5 hydrocarbons in the estuarine fresh waters is comparable with the high methane concentration (2–3 μl/l), drastically decreases in the zone of water mixing, and then rapidly increases to values several times higher than the methane concentration in seawater outside the outer boundary of the sedimentation depocenter of riverine particulate matter. A direct correlation was established for the concentration of the C4 + C5 homologues with the OM of the water mass, and the leading role was demonstrated to be played by labile OM of the autochthonous biomass (marine phytoplankton) in the genesis of higher hydrocarbon gases (alkenes, alkanes, and isoalkanes) during the early diagenetic stage of OM transformations in water. Along with the biomass of phytoplankton, a significant role in the genesis of C2–C3 hydrocarbons is played by destruction products of terrigenous OM. The destruction of OM and generation of gaseous hydrocarbons, including methane, are restricted to the pycnocline and the water-sediment interface. The absolute predominance of the sum of the C4 + C5 homologues in the hydrocarbon C2+ gases and the presence of unsaturated C2–C4 hydrocarbons are typical of the natural background of hydrocarbons of the Kara Sea water mass.  相似文献   

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