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1.
Combustion produces a complex mixture of polycondensed aromatic compounds known as black carbon (BC). Such products can become remobilized from char and soil in the form of dissolved BC (DBC). Ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI–FT-ICRMS) analysis of a variety of soil and char leachates showed that a significant proportion of DBC compounds contained one or more nitrogen atoms. While the presence of black nitrogen (DBN) in dissolved organic matter (DOM) has been reported, its molecular features were uncharacterized. Here we present results of FT-ICRMS characterization of DBN, where assigned formulae were validated on the basis on their 13C isotope signatures and fragmentation patterns obtained via collision induced dissociation. Possible chemical structures were assigned for several DBN formulae and suggest that nitrogen was incorporated into the core ring system as a pyrrole-type moiety. Most DBN compounds existed as part of homologous series where homologs differed by a mass corresponding to CO2, suggesting that they were polysubstituted with carboxylic acid groups. The environmental contribution of such novel, aromatic, combustion-derived nitrogen compounds with respect to global nitrogen cycling remains elusive. The biogeochemical implications of the input of such fire-derived products to aquatic ecosystems as part of climate change therefore need to be assessed.  相似文献   

2.
The transformation and mobility of charcoal in a fire-impacted watershed   总被引:3,自引:0,他引:3  
The incomplete combustion of fossil fuels and biomass has resulted in the global-scale distribution and accumulation of black carbon (BC) in the environment. Recently, the molecular identity of BC in the dissolved phase has been distinguished from that of natural organic matter. However, many of the processes that control BC cycling remain unidentified. We investigate changes in soil charcoal particle morphology and chemical composition using surface area analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, chemical oxidation, and 13C NMR spectroscopy. A comparison of soil charcoals differing in age by 100 years shows that aged charcoal has lower specific surface areas, higher BC/OC ratios, direct associations with soil minerals and microbial biomass, and a greater abundance of non-aromatic carbon. The water-soluble portion of soil charcoal and dissolved organic matter (DOM) from the watershed were also characterized by electrospray ionization mass spectrometry. Aqueous charcoal extracts are comprised mostly of condensed aromatic ring structures (CARS) which are also present in soil pore, river, and ground water samples. We present indirect evidence and a chemical rationale for a microbial BC dissolution mechanism. Furthermore, the speciation of CARS in the soil solution versus river and ground water provides molecular evidence of reactivity in the dissolved phase. The dissolution and export of soil BC are presently unmeasured fluxes with important implications for the global carbon cycle.  相似文献   

3.
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   

4.
溶解态黑碳(DBC)作为黑碳(BC)降解的中间产物,是海洋溶解有机碳碳库的重要组分,涉及全球海洋碳收支并进一步影响全球气候变化;是有色溶解有机质的重要组分,可改变水体光学环境从而对生态系统产生影响;也是一类良好的有机配体,在环境中易与金属离子形成络合物从而影响金属污染物的行为与毒性。鉴于其在气候变化、生态和环境等方面的重要影响,近年来研究者越来越关注DBC,并取得了一些基础性成果。目前,在DBC的定性认识上还存在一些模糊区域,所以DBC还没有一个明确的定义,DBC只是一个术语,特指一类由浓缩稠环母体和亲水性取代基(主要为羧基)组成的复杂有机物。在DBC的来源方面,已有证据证明BC降解能够产生DBC;但DBC很可能还存在其他来源,仍需进一步研究确认。DBC主要随水体进行迁移,并已观察到了DBC的降解现象,但目前对DBC的降解机理及速率仍不了解。在定量分析方法上,由于DBC的极性很强,且与其共存的基质相当复杂,分析DBC具有很大的挑战,其中苯多羧酸分子标志物法(BPCA)是定量分析DBC很有前景的方法之一,但目前仍存在一些难点需要解决。DBC在全球不同水体中含量变化很大,但目前的数据相当有限,不足以全面评估DBC的储量和循环周期。从DBC的定性识别、来源、迁移转化、定量分析及含量分布等方面综述DBC的研究进展,重点讨论BPCA法定量DBC的研究现状及存在问题,并展望DBC的研究方向。  相似文献   

5.
Recent studies have suggested that large rivers play important roles in mobilizing and transporting black carbon (BC) from land to the ocean. However, the influence of the Changjiang and Huanghe, the two largest rivers in China, on the fate of BC has not been determined. In this paper, we present measurements of BC in both the dissolved and particulate phases in the Changjiang and Huanghe Rivers and in the coastal waters of the East China Sea (ECS). Our results show that dissolved black carbon (DBC) accounted for 3.0 ± 0.4 % and 4.8 ± 3.6 % of the total DOC pool in the Changjiang and Huanghe Rivers and 3.4 ± 0.6 % of the DOC pool in the coast of the ECS. In addition, particulate black carbon (PBC) accounted for 13 ± 0.9 % and 22 ± 11 % of the POC pool in the Changjiang and Huanghe Rivers, respectively. We calculate that the Changjiang and Huanghe transported 4.7 × 1010 gC and 1.7 × 109 gC of DBC, and 2.0 × 1011 gC and 1.2 × 1010 gC of PBC to the ECS and Bohai Sea in 2015. The large amounts of BC transported by the two rivers represent a major sink of anthropogenically derived organic carbon and could have a significant impact on the ecosystem and carbon cycling in China’s marginal seas.  相似文献   

6.
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   

7.
This study demonstrates that wildfires/biomass combustion may be an important source of labile pyrogenic water-soluble organic matter (Py-WSOM) in aquatic systems. Spectroscopic analysis (solid char and Py-WSOM) with Fourier transform infrared spectroscopy (FTIR) indicated that the Py-WSOM extracted from two low temperature chars (one wood, one grass) was dominated by polar moieties (–OH and C–O) derived from depolymerization and fragmentation of lignocellulose. Incubation experiments under aerobic conditions with unsterilized river water suggested that Py-WSOM and associated biomarkers may have a turnover rate of the order of weeks to months, consistent with mixing and transport conditions of riverine systems. For example, pyrogenic dissolved organic carbon (Py-DOC) had a half-life of 30–40 days. Turnover rate for the combustion biomarkers was shorter, with levoglucosan and free lignin phenols having a half life around 3–4 days and polymeric lignin components 13–14 days. The latter observations contradict earlier studies of the biodegradation of dissolved lignin and point to the need for re-assessment of lignin degradation kinetics in well-mixed riverine systems, particularly when such lignin components are derived from thermally altered plant material that may exist in a form more labile than that in highly processed riverine DOM.  相似文献   

8.
Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and 13C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 × 10−3 Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 ±163 and 115 ± 47 μM, respectively. 13C-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly 13C-depleted with respect to bulk HMW DOM indicating that C4 grass inputs to the HMW DOM were not significant. It is speculated that C4 organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C3 organic matter is, because of the association of C4 organic matter with finer sediments. The predominantly aliphatic 13C NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC.  相似文献   

9.
Aureococcus anophagefferens, the pelagophyte responsible for brown tide blooms, occurs in coastal bays along the northeast coast of the United States. This species was identified in Chincoteague Bay, Maryland, in 1997 and has bloomed there since at least 1998. Time series of dissolved organic matter (DOM) concentrations and characteristics are presented for two sites in Chincoteague Bay: one that experienced a brown tide bloom in 2002 and one that did not. Characteristics of the bulk DOM pool were obtained using dissolved organic carbon (DOC) and ultraviolet-visible (UV-Vis) measurements (spectral slope and specific UV absorbance). High molecular weight DOM (HMW-DOM) was characterized in terms of DOC concentration, carbon: nitrogen (C:N) ratio, isotopic signature, and molecular-level characteristics as determined by direct temperature resolved mass spectrometry (DT-MS). Compositional changes in the DOM pool are associated with brown tide blooms, although a direct relationship between DOM characteristics and bloom development could not be confirmed. DOC measurements suggest that during the brown tide bloom, HMW-DOM was released into the surface water. UV-Vis analysis on the bulk DOM and molecular-level characterization of the HMW-DOM using DT-MS show that this material was optically active and more aromatic in nature. Based upon C:N ratio and HMW-DOC measurements, it appears that this HMW-DOM was more nitrogen enriched. Whether this material was released as exudates or was due to lysis ofA. anophagefferens could not be determined.  相似文献   

10.
雪冰中的黑碳记录研究的历史回顾   总被引:4,自引:2,他引:2  
明镜  秦大河  效存德 《冰川冻土》2005,27(4):539-544
黑碳(Blackcarbon)是一类大气气溶胶,也是重要的气候驱动因子之一,它与人类活动密切相关.迄今发现,雪冰是保存和记录历史时期黑碳变化的最好介质.根据前人对南极冰芯、格陵兰冰芯、中低纬度山地冰川冰芯以及雪坑样品中的黑碳记录的研究成果,讨论了不同研究地区雪冰中黑碳含量的变化,黑碳对气候环境突变、大气环流变化的响应,总结了人类活动与雪冰黑碳记录之间的关系.雪冰黑碳记录还可以获得如森林大火这样的特殊事件的信息.  相似文献   

11.
The various sources of pyrogenic and coalified carbon (black carbon, BC) in soil have considerable structural heterogeneity, making the quantification of BC a challenge. This study was aimed at evaluating the capability of different detection procedures to recover different types of BC from soil. We added defined quantities of urban dust (UD, NIST SRM1649a), diesel particulate matter (DPM, NIST SRM2975), charcoal, lignite, bituminous coal and wood to four topsoil samples. Mixtures were analyzed by way of chemo-thermal oxidation (CTO), thermal gradient oxidation (ThG), the benzene polycarboxylic acid method (BPCA) and mid-infrared spectroscopy (MIRS). CTO returned good quantification of soot BC in the pure DPM, yet the recovery of soot BC from soil was unsatisfactory (18–270%). ThG gave good precision but lower values for pure soot BC. It severely overestimated the BC content for all soil-standard mixtures. The BPCA method gave a low return for soot BC, but for the spiked soil it reliably detected charcoal and coalified C (69–107% avg. recovery) but underestimated soot BC (52–90% recovery of DPM). Linear coherence in specific MIR vibrations was found in one component soil-BC mixtures for each BC type. Applying these standard calibrations to multi-component mixtures allowed detecting charcoal and a quantification of soot BC (88% avg. recovery) via MIRS, but ignored the presence of diagenetic C. We see the greatest potential in differentiating soot from charcoal in soil by employing a combination of chemical and thermal oxidation and MIRS, while the differentiation from diagenetic C is not possible yet.  相似文献   

12.
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   

13.
我国四种典型土类有机碳剖面分布特征   总被引:2,自引:0,他引:2       下载免费PDF全文
刘飞  杨柯  李括  彭敏  聂海峰 《地学前缘》2011,18(6):20-26
以中国黑土、褐土、水稻土和砖红壤4种典型农田土类为研究对象,分析了不同土类有机碳、碳氮比和有机碳密度的剖面分布特征。结果表明:土壤有机碳含量随土层加深而呈现递减趋势;褐土有机碳含量最低,固碳潜力较大;黑土、砖红壤C/N比值明显高于水稻土和褐土,各类土壤耕地表层土壤C/N比值与第二次土壤普查数据相比有明显降低,有可能会影...  相似文献   

14.
Subsurface microbial oxidation of overridden soils and vegetation beneath glaciers and ice sheets may affect global carbon budgets on glacial-interglacial timescales. The likelihood and magnitude of this process depends on the chemical nature and reactivity of the subglacial organic carbon stores. We examined the composition of carbon pools associated with different regions of the Greenland ice sheet (subglacial, supraglacial, proglacial) in order to elucidate the type of dissolved organic matter (DOM) present in the subglacial discharge over a melt season. Electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry coupled to multivariate statistics permitted unprecedented molecular level characterization of this material and revealed that carbon pools associated with discrete glacial regions are comprised of different compound classes. Specifically, a larger proportion of protein-like compounds were observed in the supraglacial samples and in the early melt season (spring) subglacial discharge. In contrast, the late melt season (summer) subglacial discharge contained a greater fraction of lignin-like and other material presumably derived from underlying vegetation and soil. These results suggest (1) that the majority of supraglacial DOM originates from autochthonous microbial processes on the ice sheet surface, (2) that the subglacial DOM contains allochthonous carbon derived from overridden soils and vegetation as well as autochthonous carbon derived from in situ microbial metabolism, and (3) that the relative contribution of allochthonous and autochthonous material in subglacial discharge varies during the melt season. These conclusions are consistent with the hypothesis that, given sufficient time (e.g., overwinter storage), resident subglacial microbial communities may oxidize terrestrial material beneath the Greenland ice sheet.  相似文献   

15.
燃烧形成的黑碳粒子进入大气中可影响辐射平衡,导致全球气候变暖,其沉降在河流、湖泊、海洋、土壤等环境中对全球生物地球化学循环起到重要的作用,成为当前国际地球科学研究的热点问题。综述了黑碳的定义及排放、沉降、降解过程,并总结了其在现在及过去环境和气候系统中的重要作用与研究意义。黑碳是全球惰性有机碳库的重要组成部分,在全球慢速碳循环中发挥潜在作用。因其具有很强的吸光特性,它在区域气候变暖过程中扮演重要角色。沉降在不同地质载体中的黑碳难以降解,可以保存几百万年,为地质历史时期古气候和古环境重建研究提供重要信息。海洋沉积物过去数百万年的黑碳记录指示了天然火的演化信息,晚第四纪黄土剖面黑碳也指示了天然火的变化信息,最近千年的湖泊和冰芯黑碳记录既反映了天然火的信息,也指示人类活动的信号。未来黑碳研究应进一步关注标准测量方法,以真正理解黑碳在全球气候与环境系统中的作用。  相似文献   

16.
This project examined concentrations, composition and turnover neutral sugars in the Delaware estuary to gain insights into dissolved inorganic nitrogen (DIN) use by heterotrophic bacteria and into the lability and diagenetic state of dissolved organic material (DOM) during passage through the estuary. Dissolved free monosaccharides were not measurable (<5 nM) in the estuary whereas concentrations of dissolved combined neutral sugars (DCNS) were high, much higher than observed in oceanic waters. DCNS made up a similar fraction of dissolved organic carbon (DOC) as in the oceanic waters examined to date, and the monosaccharide composition of the DCNS pool was similar to that of oceanic waters. The composition did not vary substantially within the estuary or seasonally, but it did vary among three size fractions of the organic matter pool. Glucose was enriched in the low molecular weight fraction of DOC and in particulate material, whereas the high molecular weight DOC fraction was slightly depleted in glucose. Depletion experiments indicated that DCNS is not used extensively on the day time scale in the Delaware estuary, although freshly-produced polysaccharides may still be important carbon sources for heterotrophic bacteria. The very low concentrations of free monosaccharides in the Delaware estuary help to explain why DIN use by heterotrophic bacteria is relatively low in this estuary. Although DOC-DIN interactions in the Delaware apparently differ from oceanic waters, the portion of DOM traced by DCNS, which is thought to be the labile fraction, appears to be similar to that of oceanic DOM, suggesting that organic material in the estuary is degraded extensively before being exported to the coastal ocean.  相似文献   

17.
放射性碳同位素(14C)是含碳物质年代测定的有效手段,它的半衰期是5730年.研究了珠江口及南海沉积物碳黑的放射性碳年龄,碳黑样品采取化学氧化方法提取,用加速器质谱仪(AMS)测定珠江三角洲沉积柱中碳黑的放射性碳同位素剂量.研究结果表明,位于珠江口的钻孔3的碳黑的14C年龄是倒置的,邻近香港的钻孔30的碳黑14C年龄旱现老.新.老的趋势,而钻孔E2的碳黑的14C年龄则儿乎是不变的.碳黑的这种14C年龄的变化趋势与碳黑的来源相关,化石燃料来源的碳黑的增加使得碳黑的14C年龄偏老.  相似文献   

18.
19.
The composition and metabolic capability of bacterioplankton communities were examined over seasonal and spatial gradients and related to the source, composition, and quantity of dissolved organic matter (DOM) in the blackwater estuary Winyah Bay, Georgetown County, SC, USA and its tributary rivers. Bacterial community composition (BCC) was measured by terminal restriction fragment length polymorphism, and bacterial metabolic capability (BMC) was measured by defined substrate utilization patterns (Biolog GN2 plates). Spatial patterns were not important, despite the anticipated watershed effects and the well-documented influence of salinity gradients on estuarine bacterioplankton, but DOM, BCC, and BMC all showed varying degrees of temporal patterns; DOM-based groupings differentiated BCC samples better than spatiotemporal categories, but not BMC. BCC was closely related to properties describing DOM composition, particularly those related to DOM source (i.e., cypress swamps vs. in situ phytoplankton production, indicated by chlorophyll a, colored DOM spectral slope, α355/dissolved organic carbon (DOC), and DOC concentration), and to associated physicochemical variables, such as temperature, pH, and salinity. BMC was more strongly related to abiotic factors, such as temperature and dissolved nutrients, as well as to chlorophyll a and percent bioavailable DOC. In contrast with previous studies, BCC and BMC were significantly correlated in this highly heterotrophic estuary, suggesting that DOM source variability may select for specialist phylotypes above a background of generalists. This study, therefore, supports a causative pathway from DOM to BMC to BCC while suggesting that BCC and BMC may be simultaneously influenced by different suites of DOM characteristics and physicochemical parameters.  相似文献   

20.
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   

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