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1.
Sinking particles are the major transporter of organic carbon from surface to the deep ocean, and their chemical composition changes dramatically with depth. However, the exact mechanism controlling the chemical transformation as particles sink is not well understood, and little detail is known about the structural changes. This is mainly due to the paucity of techniques available to analyze the major macromolecular components of sinking particles. Here we applied advanced solid-state NMR techniques, including cross polarization/magic angle spinning (CPMAS), direct polarization/magic angle spinning (DPMAS), two-dimensional 1H-13C heteronuclear correlation (2D HETCOR) and 1H T1 inversion recovery, on sinking particles collected in the northwest Mediterranean Sea. The CPMAS 13C NMR spectrum of the 200-m particles is significantly different from that of the DPMAS 13C NMR spectrum: CPMAS overestimates the NCH and CHO groups, but underestimates the aliphatic components, which is attributed to the high mobility of polymethylene units. Thus DPMAS is more suitable for quantifying organic composition of sinking particles. Using 2D HETCOR with 1H spin diffusion, we estimated that the size of domains (similar structural entities either physically or chemically grouped together) in the 200-m sinking particles can be as large as tens of nanometers. The results of CPMAS 13C NMR and 1H inversion recovery on sinking particles from 200, 520 and 920 m indicate that the macromolecular heterogeneity observed in surface particles virtually disappears as particles sink into the deep ocean. This suggests that the macromolecular components at depth are different in structural composition than those in surface waters, and may be compositionally homogenized as particles sink.  相似文献   

2.
Humic substances were isolated from ocean, estuarine water and fresh water using a two column array of XAD-8 and XAD-4 resins in series. The extracted fulvic acids and XAD-4 fraction from different origins were characterized using UV–vis., molecular fluorescence, Fourier transform infrared (FTIR) spectroscopy and cross polarization magic angle spinning (CPMAS)-13C nuclear magnetic resonance (NMR) spectroscopy. The isolation procedure allowed us to obtain the necessary amount of sample for characterization, even in the case of open ocean water, which has a very low amount of dissolved organic carbon (DOC). Humic substances from the open ocean showed the lowest chromophore and fluorophore contents and showed relatively greater fluorescence at lower wavelengths than those from fresh water. FTIR and 13C NMR spectra highlighted the idea that humic substances from a marine environment have a more branched aliphatic structure and less aromatic structure than those highly influenced by terrestrial sources. The spectra also suggest that the open ocean humic substances have a higher content of olefinic carbons than aromatic- or alkyl-substituted carbons.  相似文献   

3.
Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state 13C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in 13C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in 13C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and 13C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.  相似文献   

4.
The molecular structural features of humic acid (HA) fractions isolated from recent sediments from the estuaries and continental platform along the Huelva littoral (SW Iberian Peninsula, Spain) were studied using complementary analytical tools. The approach included elemental analysis, solid state, 13C cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy (13C CP-MAS NMR), pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) and stable C and N isotopic composition (δ13C, δ15N). The results point to the presence of vascular plant matter contributing to all the HAs, even those far from the coastal area. A contribution of lignocellulose material was detected from 13C NMR signals at 152 ppm (O-aryl C), 55 ppm (methoxyl C) and 33 ppm (alkyl chain) and confirmed by the presence of lignin derived structures (methoxy phenols) in the pyrolysis chromatograms. Nevertheless, the HAs from the westernmost part of the continental platform had the lowest aromatic and the highest C-alkyl abundance (13C NMR spectroscopy). These data, combined with low C/N and high H/C values, a relative enrichment in δ13C and the presence in the pyrolysates of conspicuous n-alkyl nitrile and amide series, together with n-alkane/ene homologues, pointed towards a relevant marine (autochthonous) contribution to this sedimentary organic matter (OM). In contrast, HAs from sediments collected from the Tinto-Odiel River mouth and Guadiana Estuary areas revealed a major input of terrestrial OM. In general, the data support the idea that the HAs still contain valuable information about the signature of aliphatic and aromatic biomacromolecules contributing to the deposited OM.  相似文献   

5.
Time-series Mark VII sediment trap was deployed at 72°58.55′E, 62°28.63°S (north of the Prydz Bay, Antarctica) during the cruise of CHINARE-15 in cooperation with University of Marine of America. Seasonal variability of deep ocean particle fluxes and biogenic components were investigated in order to reveal the fluxes and biogeochemistry of sinking particles in the deep ocean. The results show that the total mass flux of sinking particles at a water depth of 1000 m ranges from 13.00 to 334.59 mg⋅d−1⋅m−2). A marked seasonal variability exists in the fluxes of all particle components reflecting the seasonal changes in upper water productivity. Biogenic material was a significant component and biogenic silica represented more than 80% of the biogenic matter, reflecting a diatom dominated system, but a lithogenic fraction is always present. The fact that the POC dominated over particulate inorganic carbon (as CaCO3) and Cinorg/Corg was always greater than 1, indicate a net removal of CO2 from surface water by biological activity. __________ Translated from Acta Oceanologica Sinica, 2006, 5: 49–55 [译自:海洋 学报]  相似文献   

6.
Solid state 13C NMR techniques of cross polarization with magic-angle spinning, and interrupted decoupling have been employed to examine the nature of the organic matter in eight kerogen concentrates representing five Tertiary deposits in Queensland, Australia. The NMR results show that five of the kerogens have high proportions of aliphatic carbon in their organic matter and correspond to Type I–II algal kerogens. Three of the kerogens, derived from carbonaceous shales, have a high proportion of aromatic carbon in their organic matter and correspond to Type III kerogens. The fractions of aliphatic carbon in all the kerogens, regardless of type, are shown to correlate with the conversion characteristics of the corresponding raw shales during Fischer assay. Interrupted decoupling NMR results show the presence of more oxygen-substituted carbon in the carbonaceous shales, which may account for the greater CO2 evolution and phenolic materials found in the pyrolysis products of the carbonaceous shales.  相似文献   

7.
Cross polarization, magic-angle spinning 13C NMR measurements have been made on raw oil shales that represent a variety of geologic ages, origins, depositional environments and source locations. A high degree of correlation was established between the fraction of aliphatic carbon measured by 13C NMR, and the genetic potential, calculated from Fischer assay data. The correlation is independent of the type of kerogen in the raw shale, and its degree of evolution. A short discussion on the validity of various correlations between physical/chemical properties of oil shales and Fischer assay oil yields is given.  相似文献   

8.
Solid-state 1H and 13C Nuclear Magnetic Resonance (NMR) spectroscopic experiments have been performed on isolated meteoritic Insoluble Organic Matter (IOM) spanning four different carbonaceous chondrite meteorite groups; a CR2 (EET92042), a CI1 (Orgueil), a CM2 (Murchison), and the unique C2 meteorite, Tagish Lake. These solid state NMR experiments reveal considerable variation in bulk organic composition across the different meteorite group’s IOM. The fraction of aromatic carbon increases as CR2 < CI1 < CM2 < Tagish Lake. The increases in aromatic carbon are offset by reductions in aliphatic (sp3) carbon moieties, e.g., “CHx,” and “CHx(O,N).” Oxidized sp2 bonded carbon, e.g., carboxyls and ketones grouped as “CO,” are largely conservative across these meteorite groups. Single pulse (SP) 13C magic angle spinning (MAS) NMR experiments reveal the presence of nanodiamonds with an apparent concentration ranking in the IOM of CR2 < CI1 < CM2 < Tagish Lake. A pair of independent NMR experiments reveals that, on average, the aromatic moieties in the IOM of all four meteoritic IOM fractions are highly substituted. Fast spinning SP 1H MAS NMR spectral data combined with other NMR experimental data reveal that the average hydrogen content of sp3 bonded carbon functional groups is low, requiring a high degree of aliphatic chain branching in each IOM fraction. The variation in chemistry across the meteorite groups is consistent with alteration by low temperature chemical oxidation. It is concluded that such chemistry principally affected the aliphatic moieties whereas the aromatic moieties and nanodiamonds may have been largely unaffected.  相似文献   

9.
The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (13C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. 13C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CHxO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (fa), O/C and relative proportions of various carbon types estimated by 13C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.  相似文献   

10.
Long time-series studies are critical to assessing impacts of climate change on the marine carbon cycle. A 27-year time-series study in the abyssal northeast Pacific (Sta. M, 4000 m depth) has provided the first concurrent measurements of sinking particulate organic carbon supply (POC flux) and remineralization by the benthic community. Sediment community oxygen consumption (SCOC), an estimate of organic carbon remineralization, was measured in situ over daily to interannual periods with four different instruments. Daily averages of SCOC ranged from a low of 5.0 mg C m?2 day?1 in February 1991 to a high of 31.0 mg C m?2 day?1 in June 2012. POC flux estimated from sediment trap collections at 600 and 50 m above bottom ranged from 0.3 mg C m?2 day?1 in October 2013 to 32.0 mg C m?2 day?1 in June 2011. Monthly averages of SCOC and POC flux correlated significantly with no time lag. Over the long time series, yearly average POC flux accounted for 63 % of the estimated carbon demand of the benthic community. Long time-series studies of sediment community processes, particularly SCOC, have shown similar fluctuations with the flux of POC reaching the abyssal seafloor. SCOC quickly responds to changes in food supply and tracks POC flux. Yet, SCOC consistently exceeds POC flux as measured by sediment traps alone. The shortfall of ~37 % could be explained by sediment trap sampling artifacts over decadal scales including undersampling of large sinking particles. High-resolution measurements of SCOC are critical to developing a realistic carbon cycle model for the open ocean. Such input is essential to evaluate the impact of climate change on the oceanic carbon cycle, and the long-term influences on the sedimentation record.  相似文献   

11.
Complementary, double- and single-resonance solid-state (1H and 13C) nuclear magnetic resonance (NMR) experiments were performed on a solvent extracted and demineralized sample of Murchison meteorite organic macromolecule. These NMR data provide a consistent picture of a complex organic solid composed of a wide range of organic (aromatic and aliphatic) functional groups, including numerous oxygen-containing functional groups. The fraction of aromatic carbon within the Murchison organic residue (constrained by three independent experiments) lies between 0.61 and 0.66. The close similarity in cross-polarized and single-pulse spectra suggests that both methods detect the same distribution of carbon. With the exception of interstellar diamond (readily detected in slow magic angle spinning single-pulse NMR experiments), there is no evidence in the solid-state NMR data for a significant abundance of large laterally condensed aromatic molecules in the Murchison organic insoluble residue. Given the most optimistic estimation, such carbon would not exceed 10% and more likely is a fraction of this maximum estimate. The fraction of aromatic carbon directly bonded to hydrogen is low (∼30%), indicating that the aromatic molecules in the Murchison organic residue are highly substituted. The bulk hydrogen content, H/C, derived from NMR data, ranges from a low of 0.53 ± 0.06 and a high of 0.63 ± 0.06. The hydrogen content (H/C) determined via elemental analysis is 0.53. The range of oxygen-containing organic functionality in the Murchison is substantial. Depending on whether various oxygen-containing organic functional groups exist as free acids and hydroxyls or are linked as esters and ethers results in a wide range in O/C (0.22 to 0.37). The lowest values are more consistent with elemental analyses, requiring that oxygen-containing functional groups in the Murchison macromolecule are highly linked. The combined 1H and 13C NMR data reveal a high proportion of methine carbon, which requires that carbon chains within the Murchison organic macromolecule are highly branched.  相似文献   

12.
Particulate organic carbon found in sea foam and water samples from North Inlet, South Carolina, were examined for their δ13C isotopic composition. Sea foam particulate organic carbon (POC) δ13C values ranged from ?20.4 to ?24.6‰ (mean=?22.3‰) and water POC δ13C values ranged from ?21.0 to ?28.5‰ (mean= ?24.4‰). Temporal trends in sea foam and water POC indicate that δ13C values for both POC components are depleted in the colder months and enriched in the warmer months. Measurement of δ13C from potential sources for organic matter found in sea foam, combined with data on macroalgae productivity and phytoplankton biomass, indicates that macroalgae are the principal source of POC for sea foam in the colder months. In the warmer months, phytoplankton appear to be more important contributors. The observed water POC δ13C values were always depleted relative to foam POC δ13C values. This isotopic difference may result from chemical segregation during sea foam formation or may reflect DOC δ13C values from terrestrial origins.  相似文献   

13.
In mine soil, quantification of soil organic carbon (OC) derived recently from biomass decomposition is complicated by the presence of fossil (geogenic) C derived from coal, oil shale, or similar material in the overburden. The only reliable method for such measurement is 14C analysis (i.e. radiocarbon dating) using instrumentation such as accelerator mass spectrometry, which is too expensive for routine laboratory analysis. We tested two previously used and two new methods for recent C quantification and compared them with 14C AMS radiocarbon dating as a reference using a set of soil samples (n = 14) from Sokolov, Czech Republic: (i) 13C isotope ratio composition, (ii) cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) spectroscopy, (iii) near infrared spectroscopy (NIRS) coupled with partial least squares regression and (iv) Rock–Eval pyrolysis. Conventional methods for OC determination (dry combustion, wet dichromate oxidation, loss-on-ignition) were also compared to quantify any bias connected with their use. All the methods provided acceptable recent carbon estimates in the presence of mostly aliphatic fossil C from kerogen. However, the most accurate predictions were obtained with two approaches using Rock–Eval pyrolysis parameters as predictors, namely (i) S2 curve components and (ii) oxygen index (OI). The S2 curve approach is based on the lower thermal stability of recent vs. fossil organic matter. The OI approach corresponded well with 13C NMR spectra, which showed that samples rich in recent C were richer in carboxyl C and O-alkyl C. These two methods showed the greatest potential as routine methods for recent C quantification.  相似文献   

14.
Soil organic matter (SOM) is one of the earth’s largest reservoirs of actively cycled carbon and plays a critical role in various ecosystem functions. In this study, mineral soils with the same parent material and of similar approximate age were sampled from the same climatic region in Halsey, Nebraska to determine the relationship between overlying vegetation inputs to SOM composition using complementary molecular level methods (biomarker analyses and solid state 13C nuclear magnetic resonance (NMR) spectroscopy). Soil samples were collected from a native prairie and cedar and pine sites planted on the native prairie. Free and bound lipids isolated from the pine soil were more enriched in aliphatic and cutin-derived compounds than the other two soils. Cinnamyl type lignin-derived phenols were more abundant in the grassland soil than in the pine and cedar soils. Acid to aldehyde ratios (Ad/Al) for vanillyl and syringyl type phenols were higher for the pine soil indicating a more advanced stage of lignin oxidation (also observed by 13C NMR) in the soil that has also been reported to have accelerated carbon loss. In agreement with the more abundant aliphatic lipids and cutin-derived compounds, solid state 13C NMR results also indicated that the SOM of the pine soil may have received more aliphatic carbon inputs or may have lost other components during enhanced decomposition. The observed relationship between vegetation and SOM composition may have important implications for global carbon cycling as some structures (e.g. aliphatics) are hypothesized to be more recalcitrant compared to others and their accumulation in soils may enhance below ground carbon storage.  相似文献   

15.
Carbon (POC, DOC) and carbon isotopes (δ13C) within two headwater tributaries to the Xi River Basin, southwest China were analyzed to document the geochemical characteristics and sources of organic carbon (C) within basins characterized by a monsoonal climate and karst landforms. δ13 C POC value and C/N ratio data indicate that suspended soil organic carbon (SOC) was an important source of POC in both the Nanpan and Beipan rivers (i.e., the studied tributaries). However, differences in C sources exist between the Nanpan and Beipan River Basins. Higher terrestrial plants supplied a portion of the POC within the Beipan River. In contrast, the Nanpan River was characterized by an inverse correlation between POC and DOC, and a positive relationship between the δ13C values. These trends indicate that DOC within the Nanpan River was partly derived from the degradation of soil C within the water column. In addition, the interception of C by hydrological projects (e.g., dams) positioned along the Nanpan River led to higher DOC/POC ratios. In contrast, within the Beipan River δ13C DOC values range from ?20 to ?25.2 ‰ and are consistent with ratios associated with soil C, suggesting that leaching of C from catchment soil was the dominant source of DOC. Organic C in tributaries to the Beipan River may also have been derived from intense upland soil erosion, a process that resulted in the lowest DOC/POC ratios. The collected data indicate that land-use changes have potentially influenced regional- to local-scale organic C budgets within subtropical basins subjected to karstification.  相似文献   

16.
The Loihi hydrothermal plume provides an opportunity to investigate iron (Fe) oxidation and microbial processes in a system that is truly Fe dominated and distinct from mid-ocean ridge spreading centers. The lack of hydrogen sulfide within the Loihi hydrothermal fluids and the presence of an oxygen minimum zone at this submarine volcano’s summit, results in a prolonged presence of reduced Fe within the dispersing non-buoyant plume. In this study, we have investigated the potential for microbial carbon fixation within the Loihi plume. We sampled for both particulate and dissolved organic carbon in hydrothermal fluids, microbial mats growing around vents, and the dispersing plume, and carried out stable carbon isotope analysis on the particulate fraction. The δ13C values of the microbial mats ranged from −23‰ to −28‰, and are distinct from those of deep-ocean particulate organic carbon (POC). The mats and hydrothermal fluids were also elevated in dissolved organic carbon (DOC) compared to background seawater. Within the hydrothermal plume, DOC and POC concentrations were elevated and the isotopic composition of POC within the plume suggests mixing between background seawater POC and a 13C-depleted hydrothermal component. The combination of both DOC and POC increasing in the dispersing plume that cannot solely be the result of entrainment and DOC adsorption, provides strong evidence for in-situ microbial productivity by chemolithoautotrophs, including a likelihood for iron-oxidizing microorganisms.  相似文献   

17.
Anammox, the microbial anaerobic oxidation of NH4+ by NO2− to produce N2, is recognised as a key process in the marine, freshwater and soil N cycles, and has been found to be a major sink for fixed inorganic N in the ocean. Ladderane lipids are unique anammox bacterial membrane lipids used as biomarkers for such bacteria in recent and past environmental settings. However, their fate during diagenesis and early catagenesis is not well constrained. In this study, hydrous pyrolysis experiments were performed on anammox bacterial biomass and the generated aliphatic hydrocarbons, present in oil generated at 220–365 °C, were analysed. A unique class of hydrocarbons was detected, and a representative component was isolated and rigorously identified using 2D nuclear magnetic resonance (NMR) spectroscopy. It consisted of C24 to C31 branched long chain alkanes with two internal ethyl and/or propyl substituents. The alkanes were generated above 260 °C, with maximum generation at 320 and 335 °C. Their stable carbon isotopic values were depleted in 13C, similar to carbon isotope values of the original anammox lipids, indicating that they were thermal products generated from lipids of anammox bacterial biomass. A range of sediments from different geological periods where anammox may have been an important process was screened for the presence of these compounds as possible catagenetic products. They were not detected, either because the concentration was too low, or the sediments screened were too immature for them to have been generated, or because the artificially produced products of anammox lipids may not reflect the natural diagenetic and catagenetic products of ladderane lipids.  相似文献   

18.
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   

19.
In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (13C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom (Choclodinium polykrikoides) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with 13C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.  相似文献   

20.
Very little is known about the macromolecular properties of biomass combustion residues referred to as black carbon (BC). Pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) was performed on: (i) peat from Spain at 400–1200 °C to investigate the effect of charring on pyrolysis fingerprint and (ii) natural charcoal from Laos in order to link molecular information to published chemical and reactivity parameters. Confirming earlier Py-GC/MS studies, the BC in the artificially charred peat and the natural charcoal produced predominantly benzene, toluene, C2-benzenes, PAHs and benzonitriles. Furthermore, some charcoal samples produced significant amounts of phenols, methoxyphenols, carbohydrate markers, n-alkanes and n-alkenes upon pyrolysis, reflecting non-charred and weakly charred biomass. A series of pyrolysis product ratios related to the degree of dealkylation of the pyrolysis products (benzene/toluene, naphthalene/C1-naphthalenes, C1-naphthalenes/C2-naphthalenes, benzofuran/C1-benzofurans and benzonitrile/C1-benzonitrile) increased with increasing artificial charring (peat) and, for the natural charcoal, these ratios were in accordance with established chemical and reactivity parameters related to charring intensity from other methods: proportion of aromatic C obtained from solid state 13C nuclear magnetic resonance spectroscopy (NMR), the proportion of charred material as estimated from NMR in conjunction with a molecular mixing model (NMR–MMM) and the resistance to acid dichromate oxidation. The alkyl side chains of aromatic pyrolysis products are probably inherited from short chain aliphatic C chains that cross link the predominantly aromatic building blocks of BC, and these linkages seem to disappear with increasing charring intensity. Thus, the degree of thermal alteration of BC can be discerned from the pyrolysis fragmentation pattern.  相似文献   

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