Formation Of Humic-like Substances Research Articles

Molecular-level transformations of biomass burning-derived water-soluble organic carbon during dark aqueous OH oxidation: Insights from absorption, fluorescence, high-performance size exclusion chromatography and high-resolution mass spectrometry analysis

Biomass burning (BB) releases large amounts of water-soluble organic carbon (WSOC), which would undergo heterogenous oxidation processes that induce transformations in both molecular structures and compositions within BB WSOC. This study designed an aqueous oxidation initiated by OH radicals in the absence of light for WSOC extracted from smoke particles generated by burning of corn straw and fir wood. The BB WSOC was comprehensively characterized using a combination of UV–visible spectra, excitation-emission matrix fluorescence in conjunction with parallel factor analysis (EEM-PARAFAC), high-performance size exclusion chromatography (HPSEC), and high-resolution mass spectrometry (HRMS) analyses. Over the course of oxidation, both chromophores and fluorophores exhibited gradual decreases. Moreover, EEM-PARAFAC revealed a preferential degradation of larger-sized protein-like/phenol-like organic matters, accompanied by the accumulation and/or formation of humic-like substances in aged BB WSOC. HPSEC analysis showed notable changes in molecular weight (MW) distributions for both types of BB WSOC during oxidation. Specifically, high MW species (>1 kDa) displayed a tendency to form along with oxidation, possibly attributed to the formation of assemblies via intermolecular weak forces. After oxidation, evidence of CHO compound degradation and enrichment/formation of CHON compounds was observed for both types of BB WSOC. Remarkably, the resistant, degraded and produced molecules for BB WSOC were dominated by CHO (38–73 %) and lignin-like molecules (41–47 %), suggesting diverse responses to oxidation within these two groups. Furthermore, polyphenols experienced selective degradation, while CHON, aliphatic and poly-aromatic molecules tended to form during the oxidation process for both types of BB WSOC. In summary, this study provides a comprehensive understanding of the molecular-level transformations undergone by BB WSOC during dark aqueous OH oxidation. The findings significantly contribute to our insights into atmospheric evolution of BB WSOC, thereby playing a crucial role in accurately assessing their effects within climate models and informing policy decisions.

Formation of Humic-Like Substances during the Technological Process of Lignohumate® Synthesis as a Function of Time

The composition, structure, and biological activity of humic-like substances (HLS) synthesized in the process of lignosulfonate conversion for the production of the humic product Lignohumate® (LH) were examined. It is shown that during the hydrolytic-oxidative process, the transformation of raw material and accumulation of HLS occur. Data on the chemical (elemental content, functional groups, FTIR) and spectral (absorbance and fluorescence) parameters and biological activity (in phytotest) combined with PCA show that the LH samples can be divided into three groups, depending on the duration of synthesis: initial raw material (0-time sample); “young” HLS (15–30 min), and “mature” HLS in 45–120 min of treatment. During the first 30 min, reactions similar to the ones that occur during lignin humification in nature take place: depolymerization, oxidative carboxylation, and further polycondensation with the formation and accumulation of HLS. After 45–60 min, the share of HLS reaches a maximum, and its composition stabilizes. Biological activity reaches a maximum after 45–60 min of treatment, and at that stage, the further synthesis process can be stopped. Further processing (up to 2 h and more) does not provide any added value to the humic product.

Effect of clay on greenhouse gas emissions and humification during pig manure composting as supported by spectroscopic evidence

To evaluate the effect of clay on greenhouse gas (GHGs) emissions and humification during pig manure (PM) composting, two lab-scale composting experiments, a control and a 10% clay treatment, were established. The results showed that adding clay reduced the emissions of CH4 and N2O by 45.88% and 86.79%, respectively, promoted the degradation of organic matter (OM) and facilitated the synthesis of humic acid (HA). The spectrum of dissolved organic matter (DOM) indicated that adding clay promoted the formation of aromatic carbon compounds and the degradation of aliphatic carbon. Furthermore, compared with the control, the spectral parameters including the specific UV absorbance at 254 nm (SUVA254), the specific UV absorbance at 280 nm (SUVA280) and the ration of the area at 435-480 nm and at 300-345 nm (A4/A1) of DOM were increased by 5.45%, 3.66% and 29.26%, respectively. Combined with the excitation - emission matrix (EEM) and the percentage fluorescence response (Pi,n), the clay amendment promoted the decomposition of tyrosine and Tryptophan and the formation of humic-like substances, and thus increased humification. The variation in the HA/fulvic acid and the humification index confirmed these results. Therefore, clay amendment is beneficial for reducing GHG emissions, promoting humification and aromatization during pig manure composting.

Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (<sup>1</sup>H-NMR) analysis and HPLC HULIS determination

Abstract. The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance (1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1 × 1012 molec OH cm−3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

Tryptophan and tryptophan-like substances in cloud water: Occurrence and photochemical fate

This work investigates the occurrence and photochemical behaviour of tryptophan (TRP) in the cloud aqueous phase. The concentrations of tryptophan, TRYptophan LIke Substances (TRYLIS) and HUmic LIke Substances (HULIS) in real cloud water, collected between October 2013 and November 2014 at the top of the puy de Dôme station, were determined using the Excitation-Emission-Matrix (EEM) technique. The amount of free and complexed tryptophan (TRP) up to 10−7 M in cloud aqueous phase was quantified by HPLC-UV-fluorescence analysis, and its photoreactivity under sun-simulated conditions was investigated in synthetic water samples mimicking cloud aqueous phase compositions (oceanic and continental origins). TRP undergoes direct photolysis, and its degradation is enhanced in the presence of naturally occurring species able to photo-generate hydroxyl radicals (HO). The polychromatic quantum yield of TRP (ϕ290−340nmTRP) is estimated to be 8.37 × 10−4 between 290 and 340 nm, corresponding to the degradation rate (RTRPd) of 1.29 × 10−11 M s−1 under our irradiation conditions. The degradation is accelerated up to 3.65 × 10−10 and 8.26 × 10−10 M s−1 in synthetic oceanic and continental cloud water samples doped with 100 μM hydrogen peroxide, respectively.Hydroxyl radical-mediated transformation leads to the generation of different functionalized and oxidized products, as well as small carboxylic acids, such as formate and acetate. Moreover, fluorescent signals of irradiated solutions indicate the formation of HULIS.

Effect of four crop straws on transformation of organic matter during sewage sludge composting

A 45-d laboratory experiment was conducted to compare the effect of four crop straws on the transformations of organic matter (OM) during composting of sewage sludge. The four crop straws included rape straw, wheat straw, maize straw and rice straw. The following parameters such as temperature, OM, humic-like substances (HS), fulvic-like acids (FA) and humic-like acids (HA) were determined. The degradation of OM and the formation of HS and HA could be described well by the first-order kinetic model, while the FA content fluctuated during composting. The maximal degradation rates of OM in the compost piles added with rape straw, wheat straw, maize straw and rice straw were 34.7, 46.9, 54.7 and 52.8%, respectively, and the final contents of HS were 118, 128, 141 and 134 g kg−1, respectively, while the humification indices were higher in the compost piles added with maize straw and wheat straw than in those with rice straw and rape straw. The results indicate that a higher hemicellulose content and a lower C/N ratio in crop straw can result in a higher rate of OM degradation and higher contents of HS, while a higher content of lignin can lead to a higher polymerization degree of humic substances in compost piles. The final compost piles added with maize straw has the highest contents of OM, total nitrogen and humus substance as well as the highest values of polymerization degree, while compost piles with rape straw have the highest potassium content and those with rice straw have the highest pH values.

Towards a better understanding of the origins, chemical composition and aging of oxygenated organic aerosols: case study of a Mediterranean industrialized environment, Marseille

Abstract. As part of the FORMES summer 2008 experiment, an Aerodyne compact time-of-flight aerosol mass spectrometer (cToF-AMS) was deployed at an urban background site in Marseille to investigate the sources and aging of organic aerosols (OA). France's second largest city and the largest port in the Mediterranean, Marseille, provides a locale that is influenced by significant urban industrialized emissions and an active photochemistry with very high ozone concentrations. Particle mass spectra were analyzed by positive matrix factorization (PMF2) and the results were in very good agreement with previous apportionments obtained using a chemical mass balance (CMB) approach coupled to organic markers and metals (El Haddad et al., 2011a). AMS/PMF2 was able to identify for the first time, to the best of our knowledge, the organic aerosol emitted by industrial processes. Even with significant industries in the region, industrial OA was estimated to contribute only ~ 5% of the total OA mass. Both source apportionment techniques suggest that oxygenated OA (OOA) constitutes the major fraction, contributing ~ 80% of OA mass. A novel approach combining AMS/PMF2 data with 14C measurements was applied to identify and quantify the fossil and non-fossil precursors of this fraction and to explicitly assess the related uncertainties. Results show with high statistical confidence that, despite extensive urban and industrial emissions, OOA is overwhelmingly non-fossil, formed via the oxidation of biogenic precursors, including monoterpenes. AMS/PMF2 results strongly suggest that the variability observed in the OOA chemical composition is mainly driven in our case by the aerosol photochemical age. This paper presents the impact of photochemistry on the increase of OOA oxygenation levels, formation of humic-like substances (HULIS) and the evolution of α-pinene SOA (secondary OA) components.

Enhanced humification by carbonated basic oxygen furnace steel slag – II. Process characterization and the role of inorganic components in the formation of humic-like substances

Enhanced humification by abiotic catalysts is a potentially promising supplementary composting method for stabilizing organic carbon from biowastes. In this study, the role of steel slag in the transformation of humic precursors was directly characterized by measuring the variance in dissolved organic carbon (DOC), spectroscopic parameters (E600), and the concentration and molecular weight change of humic-like substances (HLS) during the process. In addition, a mechanistic study of the process was explored. The results directly showed that steel slag greatly accelerated the formation of HLS. The findings indicate that Fe(III)-and Mn(IV)-oxides in steel slag act as oxidants and substantially enhance the polycondensation of humic precursors. Moreover, the reaction appears to suppress the release of metals from steel slag to a certain extent under acidic conditions. This can be attributed to the cover of HLS on the external surface of steel slag, which is significant for its environmentally sound reuse.

Effect of different fractions of weathered pumice in the formation of humic-like substances

AbstractPolycondensation reactions between amino acids and phenols are one of the pathways for the formation of humic substances, and clay minerals are able to catalyse these reactions. To investigate the catalytic power of allophane, an allophane fraction (ALF) was separated from weathered pumice (WP) that contained imogolite as an impurity by taking advantage of differences in sedimentation velocity. The iron content in the separated ALF was increased by up to 3.0% compared to that in the starting WP (1.3%), and the ALF was further treated with sodium dithionate and citric acid (ALF-DC) to remove the iron. The catalytic powers of WP, ALF and ALF-DC were evaluated, based on the degree of darkening of reaction mixtures from polycondensation reactions between catechol and tryptophan, model compounds for precursors of humic substances. The catalytic power for ALF was significantly higher than the corresponding values for WP and ALF-DC. This can be attributed to the high iron content of the ALF, which serves as a Lewis acid that can enhance nucleophilic reactions which occur during the polycondensation reactions.

Evidence for Organosulfates in Secondary Organic Aerosol

Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of alpha-pinene and isoprene, in the presence or absence of sulfate seed aerosol, is investigated through a series of controlled chamber experiments in two separate laboratories. By using electrospray ionization-mass spectrometry, sulfate esters in SOA produced in laboratory photooxidation experiments are identified for the first time. Sulfate esters are found to account for a larger fraction of the SOA mass when the acidity of seed aerosol is increased, a result consistent with aerosol acidity increasing SOA formation. Many of the isoprene and alpha-pinene sulfate esters identified in these chamber experiments are also found in ambient aerosol collected at several locations in the southeastern U.S. It is likely that this pathway is important for other biogenic terpenes, and may be important in the formation of humic-like substances (HULIS) in ambient aerosol.

Synthesis of Humic-like Substances Under Sterile and Non-sterile Conditions in Presence of Quartz and Volcanic Ash

This study reports on the formation of Maillard compounds (humic-like substances called “melanoidins”) from D-glucose and L-tyrosine in the presence of volcanic ash and pure quartz. It was demonstrated that the synthesis occurred not only under non-sterile, but also under sterile conditions, and under moisture and temperature stress. The temperature remained for 30 days at 70°C for 63% of the time. The non-sterile environment with a contact time of at least 30 days was the most favorable condition for the synthesis. In sterile environment, only low molecular weight polymers were formed, while in non-sterile systems high molecular weight substances were synthesized. The presence and the nature of mineral substrates appeared important even if not essential for the formation of humic-like substances. In fact, these substances were also formed by the reaction of the precursors alone.

Influence of clay minerals and exchangeable cations on the formation of humic-like substances (melanoidins) from D-glucose and L-tyrosine

AbstractThe ability to produce humic-like polymeric compounds, with D-glucose and L-tyrosine as starting materials, was evaluated in different mineral systems: (1) Ca-, Al- and Cu(II)-saturated montmorillonite; (2) Ca-, Al- and Cu(II)-saturated kaolinite; (3) quartz in the presence of two different amounts of the same cations (according to the cation exchange capacity of the clays); and (4) untreated quartz (as control). All systems proved to be effective in the formation of humic-like compounds, particularly quartz, in the presence of cations. The effectiveness in promoting humification reactions was strictly related to the amounts of added cations. In the reaction conditions considered, the humification appears to be due more to the cations than to the type of clay minerals. The clayey systems synthesized more complex (aromatic) substances than the quartz ones.

Formation of Humic-like Substances in Mixed and Pure Cultures of Aquatic Microorganisms

A natural decay of plant and animal biomass in aquatic environments results in the release of different simple structured organic substances into water. In our laboratory experiments we investigated whether some of them, e.g., starch or peptone, and also a complex yeast biomass can be transformed into humic-like substances by natural assemblages and some pure cultures of aquatic microorganisms. After a 6 months incubation most of the cultural media enriched with those natural organic substrates turned dark in color and humic-like substances (HS) could be isolated. However, the original substrate organic carbon was mainly mineralized in microbial cultures, and only about 3 % C was converted into HS. Total yields of HS differed in dependence of the individual substrate used (peptone > yeast > starch), the origin of inoculum (river > lake > groundwater), and the incubation temperature (20°C > 10°C). According to their elemental composition, and their spectroscopical and electrophoretic characteristics the microbially formed HS resembled natural aquatic humic matter, but were higher in aliphatic constituents (carbohydrates, peptides) and lower in aromatic structures. HS-like substances were also obtained from pure cultures of a bacterium Bacillus sphaericus and a fungus Cladosporium cladosporioides. The 13C and 15N isotopic contents of the microbially produced HS differed in dependence on the microbial inoculum and the type of organic substrates used, but in general they indicated anabolic processes to be mainly responsible for the humification of the simple organic substrates used in our experiments. Bildung huminstoffartiger Substanzen in Misch- und Reinkulturen aquatischer Mikroorganismen Der natürliche Abbau pflanzlicher und tierischer Biomasse in Gewässern führt zur Freisetzung einfacher organischer Stoffe ins Wasser. Die Humifizierung solcher Substanzen wie Stärke und Pepton und auch der komplexen Mikrobenbiomasse durch Misch- und Reinkulturen aquatischer Mikroorganismen wurde unter Laborbedingungen untersucht. Nach einer Inkubationszeit von 6 Monaten verfärbten sich die mit den einzelnen Substraten angereicherten Kulturen dunkel, und huminstoffähnliche Substanzen (HS) konnten isoliert werden. Der substrateigene organisch gebundene Kohlenstoff wurde allerdings überwiegend mineralisiert und nur zu ca. 3 % in HS umgewandelt. Die Gesamtausbeuten der HS unterschieden sich je nach dem eingesetzten Substrat (Pepton > Hefe > Stärke), der Herkunft des Inokulums (Flußwasser > Seewasser > Grundwasser) und der Inkubationstemperatur (20°C > 10°C). In ihrer elementaren Zusammensetzung sowie ihren spektroskopischen und elektrophoretischen Eigenschaften waren die mikrobiell gebildeten HS den natürlichen aquatischen Huminstoffen ähnlich. Sie enthielten jedoch mehr aliphatische (Kohlenhydrate, Peptide) und weniger aromatische Bestandteile. Auch in Reinkulturen des Bakteriums Bacillus sphaericus und des Pilzes Cladosporium cladosporioides wurden HS gebildet. Die 13C- und 15N-Isotopengehalte mikrobiell gebildeter HS variierten in Abhängigkeit von dem mikrobiellen Inokulum und dem organischen Ausgangssubstrat. Sie zeigten jedoch an, daß die Humifizierung der verwendeten organischen Substrate einen anabolischen Prozeß darstellt.

Formation of Humic-like Substances in Mixed and Pure Cultures of Aquatic Microorganisms

en

Influence of Clay Minerals and Exchangeable Cations on the Formation of Humic-Like Substances (Melanoidins) from D-glucose and L-tyrosine

The ability to produce humic-like polymeric compounds, with D-glucose and L-tyrosine as starting materials, was evaluated in different mineral systems: (1) Ca-, Al- and Cu(II)-saturated montmorillonite; (2) Ca-, Al- and Cu(II)-saturated kaolinite; (3) quartz in the presence of two different amounts of the same cations (according to the cation exchange capacity of the clays); and (4) untreated quartz (as control). All systems proved to be effective in the formation of humic-like compounds, particularly quartz, in the presence of cations. The effectiveness in promoting humification reactions was strictly related to the amounts of added cations. In the reaction conditions considered, the humification appears to be due more to the cations than to the type of clay minerals. The clayey systems synthesized more complex (aromatic) substances than the quartz ones.

Formation of Humic-Like Substances by Fungi Epiphytic on Spartina alterniflora

In laboratory experiments, two fungi that commonly colonize leaves of Spartina aZterniJEoru(L oisel.) were studied to determine if they contribute to the formation of humic substances, which have been isolated earlier from salt marsh estuaries. In incubations of up to one year in duration, Phaeosphaeria spartinicola and Phaeosphaeria halima did not form dark pigments when grown in an artificial, full-nutrient medium. However, if the nutrient solution was enriched with a water extract of S. alterniJEoro, appreciable amounts of dark brown substances were produced. Elemental (C, H, N, 0) and spectral (ultraviolet, visible, and Fourier Transform Infrared) analyses of these dark brown substances show them to be similar to salt marsh humic substances.