Water-soluble Organic Matter Fractions Research Articles

Water Solubility Distribution of Organic Matter Accounts for the Discrepancy in Hygroscopicity among Sub- and Supersaturated Humidity Regimes.

Water uptake properties of organic matter (OM) are critical for aerosol direct and indirect effects. OM contains various chemical species that have a wide range of water solubility. However, the role of water solubility on water uptake by OM has poorly been investigated. We experimentally retrieved water solubility distributions of water-soluble OM (WSOM) from combustion of mosquito coil and tropical peat using the 1-octanol-water partitioning method. In addition, hygroscopic growth and cloud condensation nuclei (CCN) activity of solubility-segregated WSOM were measured. The dominant fraction of WSOM from mosquito coil smoldering was highly soluble (water solubility (S) > 10-2 g cm-3), while that from peat combustion contained ∼40% of less-soluble species (S < 10-3 g cm-3). The difference in water solubility distributions induced changes in the roles of less water-soluble fractions (S < 10-3 g cm-3) on CCN activity. Namely, the less water-soluble fraction from mosquito coil combustion fully dissolved at the point of critical supersaturation, while that for tropical peat smoldering was limited by water solubility. The present result suggests that water solubility distributions of OM, rather than its bulk chemical property, need to be quantified for understanding the water uptake process.

Optical properties, molecular characterizations, and oxidative potentials of different polarity levels of water-soluble organic matters in winter PM2.5 in six China's megacities

Humic-like substances (HULIS) accounted for a great fraction of water-soluble organic matter (WSOM) in PM2.5, which efficiently absorb ultraviolet (UV) radiation and pose climate and health impacts. In this study, the molecular structure, optical properties, and oxidative potential (OP) of acid- and neutral-HULIS (denoted as HULIS-a, and HULIS-n, respectively), and high-polarity WSOM (HP-WSOM) were investigated in winter PM2.5 collected at six China's megacities. For both carbon levels and optical absorption coefficients (babs_365), HULIS-a/HULIS-n/HP-WSOM showed significant spatial differences. For each city, the carbon levels and babs_365 follow a similar order of HULIS-n > HULIS-a > HP-WSOM. Besides, the babs_365 of HULIS-n and HULIS-a showed the same order of Harbin > Beijing ≈ Wuhan > Xi'an > Guangzhou > Chengdu, while HP-WSOM exhibited an order of Wuhan > Chengdu > Xi'an > Harbin > Beijing > Guangzhou. Both HULIS-a and HULIS-n were abundant in aromatic and aliphatic compounds, whereas HP-WSOM was dominated by a carboxylic acid group. The OP (in unit of nmol H2O2 μg−1C) followed the order of HP-WSOM > HULIS-a > HULIS-n in all the cities. The OPs of HULIS-a, HULIS-n, and HP-WSOM in Harbin and Beijing were much higher than those of other cities, attributing to the high contribution from biomass burning. Highly positive correlations between reactive oxygen species (ROS) of HULIS-a and MAE365 were obtained in Chengdu, Wuhan, and Harbin, but ROS of HULIS-n had stronger correlation with MAE365 in Harbin, Chengdu, and Xi'an.

Distinctive Sources Govern Organic Aerosol Fractions with Different Degrees of Oxygenation in the Urban Atmosphere.

Understanding how the sources of an atmospheric organic aerosol (OA) govern its burden is crucial for assessing its impact on the environment and adopting proper control strategies. In this study, the sources of OA over Beijing were assessed year-around based on the combination of two separation approaches for OA, one from chemical fractionation into the high-polarity fraction of water-soluble organic matter (HP-WSOM), humic-like substances (HULIS), and water-insoluble organic matter (WISOM), and the other from statistical grouping using positive matrix factorization (PMF) of high-resolution aerosol mass spectra. Among the three OA fractions, HP-WSOM has the highest O/C ratio (1.36), followed by HULIS (0.56) and WISOM (0.17). The major sources of different OA fractions were distinct: HP-WSOM was dominated by more oxidized oxygenated OA (96%); HULIS by cooking-like OA (40%), less oxidized oxygenated OA (27%), and biomass burning OA (21%); and WISOM by fossil fuel OA (77%). In addition, our results provide evidence that mass spectral-based PMF factors are associated with specific substructures in molecules. These structures are further discussed in the context of the FT-IR results. This study presents an overall relationship of OA groups monitored by chemical and statistical approaches for the first time, providing insights for future source apportionment studies.

Impact of biogenic emissions of organic matter from a cool-temperate forest on aerosol optical properties

Abstract Terrestrial biogenic emissions of organic matter can affect the optical properties of atmospheric aerosols and thus impact the radiation budget. To investigate this, the chemical parameters of submicrometer water-soluble aerosols (WSA) collected on filters were compared to optical properties measured by a sky radiometer at a cool-temperate forest site in northern Japan. From June to December 2015, the WSA samples were collected within the forest canopy, while aerosol optical depth (AOD), single scattering albedo (SSA), absorption Angstrom exponent (AAE), and scattering Angstrom exponent (SAE) were retrieved above the canopy. The optical properties were compared with the filter-based chemical parameters only when the vertical transport of aerosol particles from the forest canopy to the air above it was significant. The result showed that the AOD and the mass concentrations of WSA exhibited similar and distinct seasonal variations with peaks in summer and autumn. In summer, sulfate accounted for 60% of the mass of WSA, which was linked to a high SSA (>0.95), low AAE (1.15 ± 0.84), and low SAE (1.25 ± 0.22). In contrast, water-soluble organic matter (WSOM) accounted for 70% of the mass of WSA in autumn. This large fraction of WSOM was associated with a decrease in SSA (0.90–0.95) and an increase in AAE (2.45 ± 0.91) and SAE (1.46 ± 0.15). The results suggest that in summer, aerosol particles with a greater size range corresponded to aerosol chemical compositions dominated by sulfate. In contrast, smaller particles with a strong light absorption at shorter wavelengths, were likely important in autumn and associated with a composition dominated by WSOM. The majority of WSOM in autumn has previously been associated with emissions of α-pinene from the forest floor and the subsequent formation of biogenic secondary organic aerosols (BSOA). This study indicates that α-pinene-derived SOAs, mostly originating from the forest floor, were associated with a summer to autumn decrease in SSA. This process can modulate the radiative effect on a regional scale.

Content of water-soluble carbohydrates as a quality indicator of cryogenic soils

The content of water-soluble organic matter in the soil is an important indicator of its quality and affects physical, chemical and biological properties of soil. This indicator is widely used for assessment of most zonal soils. However, in some cases, accumulation rates of water-soluble organic compounds in soil may significantly exceed the rate of their destruction. If so, it is more important to quantify not only the fraction of water-soluble organic matter as a whole but also to determine its composition. In this context, it is important to determine the content of the most labile and available for microorganisms compound – water-soluble carbohydrates. In this paper, the content of water-soluble carbohydrates and water-soluble organic matter in soils of Coastal Antarctica was estimated. Soils under three different plant communities were studied. We found that water-soluble organic matter of studied soils may contain up to 50% of carbohydrates. Hence, further research is needed to study other soils of Coastal Antarctica to determine their vulnerability to global climate change

Optical properties, source apportionment and redox activity of humic-like substances (HULIS) in airborne fine particulates in Hong Kong

Humic-like substances (HULIS) account for a considerable fraction of water-soluble organic matter (WSOM) in ambient fine particulates (PM2.5) over the world. However, systemic studies regarding the chemical characteristics, sources and redox activity of HULIS are still limited. In this study, the mass concentration, optical properties, and reactive oxygen species (ROS)-generation potential of HULIS were investigated in PM2.5 samples collected in Hong Kong during 2011–2012, and they all showed higher levels on days under regional pollution than on days under long range transport (LRT) pollution and local emissions. Positive matrix factorization (PMF) analysis was conducted regarding the mass concentration and dithiothreitol (DTT) activity of HULIS. Four primary sources (i.e. marine vessels, industrial exhaust, biomass burning, and vehicle emissions), and two secondary sources (i.e. secondary organic aerosol formation and secondary sulfate) were identified. Most sources showed higher contributions to both the mass concentration and DTT activity of HULIS on regional days than on LRT and local days, except that marine vessels had a higher contribution on local days than the other two synoptic conditions. Secondary processes were the major contributor to HULIS (54.9%) throughout the year, followed by biomass burning (27.4%) and industrial exhaust (14.7%). As for the DTT activity of HULIS, biomass burning (62.9%) and secondary processes (25.4%) were found to be the top two contributors. Intrinsic ROS-generation potential of HULIS was also investigated by normalizing the DTT activity by HULIS mass in each source. HULIS from biomass burning were the most DTT-active, followed by marine vessels; while HULIS formed through secondary processes were the least DTT-active. For the optical properties of HULIS, multiple linear regression model was adopted to evaluate the contributions of various sources to the light absorbing ability of HULIS. Biomass burning was found to be the only source significantly associated with the light absorbing property of HULIS.

Polarity-Dependent Chemical Characteristics of Water-Soluble Organic Matter from Laboratory-Generated Biomass-Burning Revealed by 1-Octanol-Water Partitioning.

Polarity distribution of water-soluble organic matter (WSOM) is an important factor in determining the hygroscopic and cloud nucleation abilities of organic aerosol particles. We applied a novel framework to quantitatively classify WSOM based on the 1-octanol-water partition coefficient (KOW), which often serves as a proxy of polarity. In this study, WSOM was generated in a laboratory biomass-burning experiment by smoldering of Indonesian peat and vegetation samples. The fractionated WSOM was analyzed using a UV-visible spectrophotometer, spectrofluorometer, and time-of-flight aerosol chemical speciation monitor. Several deconvolution methods, including positive matrix factorization, parallel factor analysis, and least-squares analysis, were applied to the measured spectra, resulting in three classes of WSOM. The highly polar fraction of WSOM, which predominantly exists in the range of log KOW < 0, is highly oxygenated and exhibits similar optical properties as those of light-absorbing humic-like substances (HULIS, termed after the humic substances due to the similarity in chemical characteristics). WSOM in the least-polar fraction, which mainly distributes in log KOW > 1, mostly consists of hydrocarbon-like and high molecular weight species. In between the most- and least-polar fraction, WSOM in the marginally polar fraction likely contains aromatic compounds. The analyses have also suggested the existence of HULIS with different polarities. Comparison with previous studies indicates that only WSOM in the highly polar fraction (log KOW < 0) likely contributes to water uptake.

Hygroscopic growth of particles nebulized from water-soluble extracts of PM2.5 aerosols over the Bay of Bengal: Influence of heterogeneity in air masses and formation pathways

Hygroscopic properties of water-soluble matter (WSM) extracted from fine-mode aerosols (PM2.5) in the marine atmospheric boundary layer of the Bay of Bengal (BoB) have been investigated during a cruise from 27th December 2008 to 30th January 2009. Hygroscopic growth factors were measured on particles generated from the WSM using an H-TDMA system with an initial dry size of 100nm in the range of 5–95% relative humidity (RH). The measured hygroscopic growth of WSM at 90% RH, g(90%)WSM, were ranged from 1.11 to 1.74 (mean: 1.43±0.19) over the northern BoB and 1.12 to 1.38 (mean: 1.25±0.09) over the southern BoB. A key finding is that distinct hygroscopic growth factors are associated with the air masses from the Indo-Gangetic plains (IGP), which are clearly distinguishable from those associated with air masses from Southeast Asia (SEA). We found higher (lower) g(90%)WSM over the northern (southern) BoB, which were associated with an IGP (SEA) air masses, probably due the formation of high hygroscopic salts such as (NH4)2SO4. On the other hand, biomass burning influenced SEA air masses confer the low hygroscopic salts such as K2SO4, MgSO4, and organic salts over the southern BoB. Interestingly, mass fractions of water-soluble organic matter (WSOM) showed negative and positive correlations with g(90%)WSM over the northern and southern BoB, respectively, suggesting that the mixing state of organic and inorganic fractions could play a major role on the g(90%)WSM over the BoB. Further, WSOM/SO42− mass ratios suggest that SO42− dominates the g(90%)WSM over the northern BoB whereas WSOM fractions were important over the southern BoB. The present study also suggests that aging process could significantly alter the hygroscopic growth of aerosol particles over the BoB, especially over the southern BoB.

Profiling Water-Soluble Organic Matter from Urban Aerosols Using Comprehensive Two-Dimensional Liquid Chromatography

Comprehensive two-dimensional liquid chromatography (LC×LC) coupled with a diode array detector (DAD) has been used for the first time to investigate chemical heterogeneity and map the hydrophobicity versus molecular weight distribution of the most hydrophobic acid fractions in water-soluble organic matter (WSOM) from fine atmospheric aerosols collected over different seasons at a urban location. The use of LC×LC–DAD, combining the use of two independent separation mechanisms (per aqueous liquid chromatography [PALC] versus size-exclusion chromatography [SEC]), has shown a great potential for unraveling and resolving the heterogeneity of WSOM, further providing a deeper insight into how size-distinguished aerosol WSOM fractions differ in hydrophobicity during different seasonal events. The combination of PALC×SEC–DAD data with an already proposed data treatment procedure revealed that the WSOM samples collected during warm seasons are enriched in aliphatic structures, while those collected during colder s...

Molecular characteristics of the water soluble organic matter in size-fractionated aerosols collected over the North Atlantic Ocean

Size-fractionated aerosol impactor samples (n=3) representing North American, North African, and marine air mass influences were collected over the North Atlantic Ocean as part of the 2011 US GEOTRACES cruise (GEOTRACES GA03), and a molecular-level chemical characterization of the water soluble organic matter (WSOM) was obtained using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Remarkable differences were found between the molecular characteristics of WSOM from the fine (<0.49μm) and coarse size fractions demonstrating the importance of collecting size-fractionated aerosols in order to obtain a full molecular characterization of aerosol WSOM. The greatest molecular complexity, as defined by the number of formulas in each fraction, was found in the <0.49μm fraction of North American and North African-influenced aerosols, and in the >7.2μm fraction of marine-influenced aerosols. Principal component analysis (PCA) showed the <0.49μm fraction of the North American-influenced WSOM to be differentiated from all other size fractions by the prevalence of highly oxidized compounds, an indicator of atmospheric aging. The coarse fractions of the North American-influenced sample showed evidence of important contributions from low O/C (<0.2) and condensed aromatic compounds indicative of primary combustion-influenced organic matter (OM). The fine fractions of the marine and North African-influenced samples showed characteristics of a primary marine biological source including peptide-like, phospholipid-like, and carbohydrate-like molecular formulas. The coarse fractions of the marine sample and the 0.49–3.0μm fraction of the North African-influenced sample were defined by molecular formulas at intermediate O/C (0.2 to 0.6) and high H/C (>1.5) ratios including many heteroatom (N, S, P) containing formulas. Condensed aromatic compounds, which originate from anthropogenic sources and can affect the global climate by absorbing solar radiation, as well as compounds that can be attributed to secondary organic aerosols (SOA), were found in all 17 WSOM fractions analyzed. This indicates the ubiquitous nature of these types of compounds across aerosol size fractions and air mass influences, even in aerosols collected over the middle of the ocean. These results provide an indication of size-fractionated aerosol composition, and future molecular characterization work should be paired with physical characteristics to inform size-fractionated and source-resolved models of aerosol OM impacts in the atmosphere.

Analysis of CCN activity of Arctic aerosol and Canadian biomass burning during summer 2008

Abstract. The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50–85° N and 40–130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66–94% by volume), with a water-soluble mass fraction of more than 50%. The aerosol hygroscopicity parameter, κ, ranged between κ = 0.08–0.32 for all air mass types. Industrial pollution had the lowest κ of 0.08 ± 0.01, while the Arctic background had the highest and most variable κ of 0.32 ± 0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar κ (0.18 ± 0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (κorg) was parameterized by the volume fraction of water-soluble organic matter (εWSOM), with a κ = 0.12, such that κorg = 0.12εWSOM. Assuming bulk (size-independent) composition and including the κorg parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, the external mixing assumption provided the best results, even though the available observations could not determine the true degree of external mixing and therefore may not always be representative of the environments sampled. No correlation was observed between κorg and O : C. A novel correction of the CCN instrument supersaturation for water vapor depletion, resulting from high concentrations of CCN, was also employed. This correction was especially important for fresh biomass burning plumes where concentrations exceeded 1.5×104 cm−3 and introduced supersaturation depletions of &amp;amp;geq;25%. Not accounting for supersaturation depletion in these high concentration environments would therefore bias CCN closure up to 25% and inferred κ by up to 50%.

Microbial respiration activities related to sequentially separated, particulate and water-soluble organic matter fractions from arable and forest topsoils

This study aimed to reveal differences in the relevance of particulate as well as water-soluble organic matter (OM) fractions from topsoils to the easily biodegradable soil organic matter (SOM). We selected eight paired sites with quite different soil types and soil properties. For each of these sites, we took samples from adjacent arable and forest topsoils. Physically uncomplexed, macro-, and micro-aggregate-occluded organic particle, as well as water-soluble OM fractions were sequentially separated by a combination of electrostatic attraction, ultrasonic treatment, density separation, sieving, and water extraction. The easily biodegradable SOM of the topsoil samples was determined by measuring microbial respiration during a short-term incubation experiment (OC R). The organic carbon (OC) contents separated by i) the physically uncomplexed water-soluble OM, ii) the macro-, and iii) the micro-aggregate-occluded organic particle as well as water-soluble OM fractions were significantly correlated with OC R. The correlation coefficients vary between 0.54 and 0.65 suggesting differences in the relevance of these OM fractions to the easily biodegradable SOM. The strongest correlation to OC R was detected for the OC content separated by the physically uncomplexed water-soluble OM indicating the most distinct relation to the easily biodegradable SOM. This was found to be independent from land use or soil properties.

Thermophilic Anaerobic Digestion of Sugar Beet Tailings

Tailings from sugar beet processing are currently managed by landfilling or land application. As an alternate option, beet tailings were anaerobically digested at thermophilic temperatures. It was found that tailings contain a large fraction of water-soluble organic matter, approximately 0.6 g COD (chemical oxygen demand) per g VS (volatile solids), that inhibited initiation of methanogenesis. This work showed that methanogenesis can be initiated if the solubilized material is removed. By using a process that involves first leaching and removal of solubilized matter followed by flooding the bed with digested leachate containing acclimatized inoculum, anaerobic digestion of the tailings was successfully accomplished. Most of the methane potential remaining in solids was generated within a week. The methane yield of tailings was estimated to be 295 L at standard temperature and pressure (STP) per kg VS, of which 50% to 60% was from the readily solubilized organic matter. A volume reduction of 70% to 80% was achieved, and approximately 60% of dry matter and 75% of volatile solids were degraded. All the volatile organic acids (acetic, propionic, and butyric) after an initial accumulation were degraded to low levels in all experiments. Individually, 53.3% of crude protein, 88.3% of nonfibrous carbohydrates, 81% of hemicellulose, 31.5% of lignin, and 64.6% of cellulose were either degraded or solubilized. It was also shown that a robust inoculum for sustained thermophilic anaerobic digestion can be cultured by initially flooding a bed of tailings with a buffer solution. The inoculum thus developed was robust enough to carry out successive balanced digestion of several batches of tailings.

Hygroscopic properties of water-soluble matter and humic-like organics in atmospheric fine aerosol

Abstract. Ambient continental-rural fine aerosol (K-puszta, Hungary, PM1.5) was sampled on quartz fibre filters in winter and summer 2001. Water-soluble matter (WSM) was extracted in MilliQ-water, and, in a second step, solid phase extraction was used to isolate the less hydrophilic fraction (ISOM) of the water-soluble organic matter (WSOM) from remaining inorganic salts and "most" hydrophilic organic matter (MHOM). This approach allowed ISOM, which constitutes the major fraction of WSOM, to be isolated from ambient aerosols and investigated in pure form. Hygroscopic properties of both WSM and ISOM extracts as well as of aquatic reference fulvic and humic acids were investigated using a Hygroscopicity Tandem Differential Mobility Analyser (H-TDMA). ISOM deliquesced between 30% and 60% relative humidity (RH), and hygroscopic growth factors at 90% RH ranged from 1.08 to 1.17. The hygroscopicity of ISOM is comparable to secondary organic aerosols obtained in smog chamber experiments, but lower than the hygroscopicity of highly soluble organic acids. The hygroscopic behaviour of investigated fulvic and humic acids had similarities to ISOM, but hygroscopic growth factors were slightly smaller and deliquescence was observed at higher RH (75-85% and 85-95% RH for fulvic acid and humic acid, respectively). These differences probably originate from larger average molecular mass and lower solubility of fulvic and humic acids. Inorganic composition data, measured ISOM hygroscopicity, and a presumed value for the hygroscopicity of the small remaining MHOM fraction were used to predict hygroscopic growth of WSM extracts. Good agreement between model prediction and measured water uptake was observed with differences (by volume) ranging from +1% to -18%. While deliquescence properties of WSM extracts were mainly determined by the inorganic salts (42-53 wt % of WSM), the WSOM accounted for a significant fraction of particulate water. At 90% RH, according to model predictions and measurements, about 80-62% of particulate water in the samples are associated with inorganic salts and about 20-38% with WSOM. The relative contributions of both distinguished WSOM fractions, ISOM and MHOM, remains uncertain since MHOM was not available in isolated form, but the results suggest that the less abundant MHOM is also important due to its presumably larger hygroscopicity.

Effect of vegetation on chemical composition of H horizons in incipient podzols as characterized by [formula omitted] NMR and pyrolysis-GC/MS

In a primary vegetation sequence on wind blown sands in the Netherlands, podzolization becomes evident under pine forest with various undergrowth and is more expressed under the subsequent beech forest. Recognizable podzol-B horizons appear together with H (humified O) horizons. In order to investigate whether the vegetation influences H horizon composition and the water-soluble fraction of this horizon, H horizons of three subsequent succession stages ( Pinus/Empetrum–Fagus/Vaccinium–Fagus without undergrowth) were sampled, fractionated, and analysed with 13 C CPMAS-NMR, pyrolysis-GC/MS, and by pollen analysis. Water soluble and NaOH soluble fractions of the three H horizons were very similar, suggesting that the humified material in the H horizon was formed exclusively from pine litter and that beech litter, yearly added to the soil surface in large amounts, did not influence the composition of the H horizon. The fact that the input of beech litter into the H horizon under beech was small was supported by very low amounts of Fagus pollen in all H layers. Humin fractions of the three H horizons were remarkably different, which was mainly due to varying amounts of beech root litter. The similarity of the water soluble organic matter fractions suggested that a direct relation between vegetation and organic matter mobilized by humification in the H horizon only exists under pine forest. Hence, increased podzolization under beech was probably not due to changing organic matter input, but to the factor time.

Composition of soil organic matter and its water‐soluble fraction under young vegetation on drift sand, central Netherlands

SummaryPodzols tend to form on drift sands in The Netherlands given sufficient time. Differences in organic matter (OM) composition relate to vegetation succession on drift sand that evolves eventually into a micropodzol. We examined the relation between the water‐soluble organic matter (WSOM) and the total OM composition in the Ah horizons of the first vegetation stages, under grass (Corynephorus canescens), moss (Polytrichum piliferum), heather (Calluna vulgaris) and pine (Pinus sylvestris), as determined by pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS) and analysis of polysaccharides after acid hydrolysis. Polysacharides dominate the OM in the Ah horizons under grass and moss. Lignin and aliphatic compounds are minor compounds in these profiles, but are more important under heather and pine. The Py‐GC traces of the WSOM under grass and moss contain abundant products derived from polysaccharides. The water‐soluble fraction is enriched in phenolic and aliphatic compounds in comparison with their contents in pyrolysates of the total OM. In the WSOM fractions under heather and pine, phenols dominate the pyrolysates, whereas lignin‐derived methoxyphenols are rare. Remarkably large amounts of alkenes and alkanes are present in the pyrolysates of these water‐soluble fractions, most probably derived from aliphatic biopolymers. Their presence in water might be explained through the formation of colloids, which are stabilized by micelle‐like arrangements.