Molecular Composition Of Organic Matter Research Articles

Molecular composition of clouds: a comparison between samples collected at tropical (Réunion Island, France) and mid-north (Puy de Dôme, France) latitudes

Abstract. The composition of dissolved organic matter of cloud water has been investigated through non-targeted high-resolution mass spectrometry on only a few samples that were mostly collected in the Northern Hemisphere in the USA, Europe and China. There remains, therefore, a lack of measurements for clouds located in the Southern Hemisphere, under tropical conditions and influenced by forest emissions. As a matter of fact, the comparison of the composition of clouds collected in different locations is challenging since the methodology for the analysis and data treatment is not standardized. In this work, the chemical composition of three samples collected at Réunion Island (REU) during the BIO-MAÏDO field campaign, in the Indian Ocean, with influences from marine, anthropogenic and biogenic (tropical) emissions, is investigated and compared to the chemical composition of samples collected at the Puy de Dôme (PUY) observatory in France. The same methodology of analysis and data treatment was employed, producing a unique dataset for the investigation of the molecular composition of organic matter in cloud water. Besides the analysis of elemental composition, we investigated the carbon oxidation state (OSC) of dissolved organic matter, finding that overall samples collected at PUY are more oxidized than those collected at REU. Molecular formulas were also classified based on stoichiometric elemental ratios, showing the high frequency and abundance of reduced organic compounds, classified as lipids (LipidC), in this matrix, which led to a search for terpene oxidation products in cloud water samples. To better discriminate between samples collected at PUY and REU, statistical analysis (principal component analysis and agglomerative hierarchical clustering) was performed on the ensemble of molecular formulas and their intensities. Samples collected at REU have a different composition from samples collected at PUY, which is mainly linked to different primary sources, the processing of organic matter in cloud water and the influence of different primary emissions at the two locations.

Arsenic biogeochemical cycling association with basin-scale dynamics of microbial functionality and organic matter molecular composition

Geogenic arsenic (As)-contaminated groundwater is a sustaining global health concern that is tightly constrained by multiple interrelated biogeochemical processes. However, a complete spectrum of the biogeochemical network of high-As groundwater remains to be established, concurrently neglecting systematic zonation of groundwater biogeochemistry on the regional scale. We uncovered the geomicrobial interaction network governing As biogeochemical pathways by merging in-field hydrogeochemical monitoring, metagenomic analyses, and ultrahigh resolution mass spectrometry (FT-ICR MS) characterization of dissolved organic matter. In oxidizing to weakly reducing environments, the nitrate-reduction and sulfate-reduction encoding genes (narGHI, sat) inhibited the dissolution of As-bearing iron minerals, leading to lower As levels in groundwater. In settings from weakly to moderately reducing, high abundances of sulfate-reduction and iron-transport encoding genes boosted iron mineral dissolution and consequent As release. As it evolved to strongly reducing stage, elevated abundance of methane cycle-related genes (fae, fwd, fmd) further enhanced As mobilization in part by triggering the formation of gaseous methylarsenic. During redox cycling of N, S, Fe, C and As in groundwater, As migration to groundwater and immobilization in mineral particles are geochemically constrained by basin-scale dynamics of microbial functionality and DOM molecular composition. The study constructs a theoretical model to summarize new perspectives on the biogeochemical network of As cycling.

Differences in Dissolved Organic Matter Molecular Composition along Two Plume Trajectories from the Yangtze River Estuary to the East China Sea.

Analyzing the molecular composition change of dissolved organic matter (DOM) during transportation in estuaries can enhance our understanding of the fate of DOM. However, the impact of hydrologic conditions resulting from large river plumes on the DOM cycle are less explored, and previous studies were insufficient to capture the molecular fate that occur during the transportation process. In this study, we used a range of bulk and optical techniques, as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), to determine the concentration and characteristics of DOM along two trajectories of downstream plumes of diluted water of the Yangtze (Changjiang) River estuary (YRE) during the high discharge season. These two plumes situated along the route of the summer Changjiang diluted water (CDW) have been identified and named CDW-North (CDW-N) and CDW-South (CDW-S), respectively. Despite having the same riverine end-member origin, the turbidity zone in YRE significantly modifies the molecular characteristics and composition of DOM. The results of FT-ICR MS indicated a spatial variation of DOM composition in the coastal zone of the two plumes. The relative intensities of the CHO, CHOS, and CHONS compounds are negatively correlated with salinity. In addition, the coastal zones of both CDW-N and CDW-S are characterized by more autochthonous DOM sources. More CHON compounds in CDW-N are probably due to the production of autochthonous DOM in offshore waters. The activity of phytoplankton increased the surface dissolved oxygen level of CDW-N in the coastal zone. However, the hypoxic zone formed at the bottom of the CDW-N due to microbial degradation of organic matter and may further benefit the preservation of CHON compounds. Our study emphasizes that the characteristics and composition of the estuarine DOM can be significantly shaped by distinct large river plumes. Furthermore, using FT-ICR MS in combination with complementary techniques can better assist in identifying the sources and transformation mechanisms of estuarine DOM in large river plume-affected systems and provide more valuable insights into the role of DOM in the estuarine biogeochemical cycle.

Soil organic matter and biogenic-abiogenic interactions in soils of Larsemann Hills and Bunger Hills, East Antarctica

Although Antarctic soils are usually described as weakly developed, recent studies indicated the significant variability in soil forming conditions across the sixth continent as well as considerable diversity of soils. The identification of pedogenetic processes in Antarctica is crucial for understanding not only the current state of its environment, but also for better understanding of soil development on Earth through time. Our study provides a detailed investigation of micromorphological features and molecular composition of organic matter of soil and soil-like bodies of remote areas of East Antarctica - Larsemann Hills and Bunger Hills, which are characterized by harsh environmental conditions. Studied soils showed predominantly coarse structure and low organic carbon content, alkaline to almost neutral pH range. Thin sections of studied soils were characterized by predominance of grains of quartz, feldspars, and other primary minerals with angular shapes indicating relatively weak degree of their alteration. All studied humic substances are characterized by the predominance of aliphatic structures. Moreover, it was observed that studied humic acids contains significant amounts of carbohydrates, polysaccharides, esters and amino acids and hydrophilic fragments predominate. Organo-mineral interactions were mostly connected with development of biofilms in the topsoil horizons with the maximal biological activity among studied soils.

Sedimentary organic matter molecular composition reveals the eutrophication of the past 500 years in Lake Daihai, Inner Mongolia

Lake eutrophication seriously threatens water quality and human health. Under continuous global warming and intensified human activity, increasing attention is being paid to how lake trophic status responds to climate change and anthropogenic impacts. Based on the sedimentary organic matter (SOM) molecular composition determined by the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) technology, and combined with the SOM stable nitrogen isotopes (δ15Norg), we studied how lake trophic status and ecology respond to both climatic changes and anthropogenic impacts of the past 500 yrs at Lake Daihai, Inner Mongolia. The results show that the relative abundance of lipids, proteins, and carbohydrates in lake sediments kept relatively low before AD ∼1850, and increased gradually thereafter, especially after AD ∼1950, suggesting that the lake trophic status was low before AD ∼1850, but obviously increased during the past one more century. On the other hand, the relative abundance of allochthonous condensed aromatics and vascular plant-derived polyphenols compounds gradually decreased after AD ∼1850, which is most likely due to the intensified land-use changes in the catchment. Our results show that the SOM molecular composition is more sensitive to trace the land-use changes than the δ15Norg ratios, suggesting a potential use of this technique to trace even earlier human land uses (e.g., during the prehistorical times) in a catchment. The results of this study suggest that intensified land-use change, increased discharges of human sewage and industrial wastewater, cropland runoff, and concentrated effects caused by lake level drops may have combinedly increased nutrient concentration and accelerated lake eutrophication at Lake Daihai. Therefore, proper policy is necessary to slow down anthropogenic impacts and limit further eutrophication for lakes like Lake Daihai.

Chronic Warming and Nitrogen-Addition Alter Soil Organic Matter Molecular Composition Distinctly in Tandem Compared to Individual Stressors

Forest soils are major reservoirs of carbon (C), but these stores are threatened by increasing global temperatures and atmospheric nitrogen (N) deposition. These environmental stressors can alter soil microbial communities and soil organic matter (SOM) biogeochemistry through a variety of mechanisms. To investigate the impact of chronic warming, N-addition, and simultaneous warming and N-addition (warming + N) on forest soils, soil samples from the Harvard Forest Soil Warming and Nitrogen Addition (SWaN) experiment were analyzed after 14 years. Elemental analysis, targeted compound analysis by gas chromatography–mass spectrometry, and 13C nuclear magnetic resonance (NMR) spectroscopy were used to analyze changes in SOM in both the organic and mineral (0–10 cm) soil layers. Overall, changes in the molecular composition and microbial biomass were observed, but the extent of differences was unique to warming, N-addition, and warming + N treatments. Specifically, N-addition slowed SOM decomposition as measured via solid-state 13C NMR, while warming and warming + N accelerated SOM decomposition. Continued SOM decomposition after 14 years with warming + N signified a pronounced change to observations made after 4 and 10 years of experimental treatment. This is also demonstrative of how a two-factor approach leads to a unique molecular-level response that cannot be predicted from experiments with individual stressors alone. This study emphasizes the need to observe environmental stressors in tandem using a combination of molecular-level approaches to obtain a comprehensive understanding of how persistent anthropogenic activity will fundamentally alter forest soil systems.

Soil Organic Matter Molecular Composition Shifts Driven by Forest Regrowth or Pasture after Slash-and-Burn of Amazon Forest

Slash-and-burn of Amazon Forest (AF) for pasture establishment has increased the occurrence of AF wildfires. Recent studies emphasize soil organic matter (SOM) molecular composition as a principal driver of post-fire forest regrowth and restoration of AF anti-wildfire ambience. Nevertheless, SOM chemical shifts caused by AF fires and post-fire vegetation are rarely investigated at a molecular level. We employed pyrolysis-gas chromatography-mass spectrometry to reveal molecular changes in SOM (0-10, 40-50 cm depth) of a slash-burn-and-20-month-regrowth AF (BAF) and a 23-year Brachiaria pasture post-AF fire (BRA) site compared to native AF (NAF). In BAF (0-10 cm), increased abundance of unspecific aromatic compounds (UACs), polycyclic aromatic hydrocarbons (PAHs) and lipids (Lip) coupled with a depletion of polysaccharides (Pol) revealed strong lingering effects of fire on SOM. This occurs despite fresh litter deposition on soil, suggesting SOM minimal recovery and toxicity to microorganisms. Accumulation of recalcitrant compounds and slow decomposition of fresh forest material may explain the higher carbon content in BAF (0-5 cm). In BRA, SOM was dominated by Brachiaria contributions. At 40-50 cm, alkyl and hydroaromatic compounds accumulated in BRA, whereas UACs accumulated in BAF. UACs and PAH compounds were abundant in NAF, possibly air-transported from BAF.

Insights into the role of the microbial community lifestyle strategies in variations of the dissolved organic matter molecular composition along an effluent-dominated river

Urbanization has dramatically changed the quality and quantity of dissolved organic matter (DOM) fluxes in rivers, thereby affecting the diversity and lifestyle strategies of microbial communities. However, relationships between DOM molecular composition and microbial lifestyle strategies in effluent-dominated rivers are poorly understood. Herein, we investigated the variations in DOM structure and composition of an effluent-dominated river and further revealed how these changes alter the abundance and lifestyle strategies of microbial communities. Results demonstrated that macromolecular (MW > 35 kDa) humic-like substances constituted the major components of effluent-dominated riverine DOM. Also, due to the degradation of humic-like substances, the accumulation of protein-like substances was observed from upstream to downstream areas, corresponding to an apparent decrease in overall aromaticity. The abundance of bacterial, Actinobacteria, and eukaryotic was higher in the upstream and midstream areas but relatively lower in the downstream area. The response of bacterial and Actinobacteria communities to the changes in DOM composition was more prominent as compared to that of eukaryotic. Based on multivariate statistical analysis, the decrease in aromatic components (MW > 35 kDa) was mainly attributed to the degradation of Proteobacteria and Actinobacteria (K-strategists), resulting in a decrease in their relative abundance along the river course. Proteins and polysaccharides (15 kDa < MW < 35 kDa, MW < 6 kDa) were more easily utilized by Firmicutes and Bacteroidetes (r-strategists), leading to an increase in their relative abundance. With the decrease of macromolecular humic-like substances and the increase of protein-like substances, river microbial communities shifted from K-strategists to r-strategists. This work unveils the evolution of DOM in an effluent-dominated river and the influence of the degradation of macromolecular humic-like substances on r/K-strategists.

Soil organic matter molecular composition with long-term detrital alterations is controlled by site-specific forest properties.

Forest ecosystems are important global soil carbon (C) reservoirs, but their capacity to sequester C is susceptible to climate change factors that alter the quantity and quality of C inputs. To better understand forest soil C responses to altered C inputs, we integrated three molecular composition published data sets of soil organic matter (SOM) and soil microbial communities for mineral soils after 20 years of detrital input and removal treatments in two deciduous forests: Bousson Forest (BF), Harvard Forest (HF), and a coniferous forest: H.J. Andrews Forest (HJA). Soil C turnover times were estimated from radiocarbon measurements and compared with the molecular-level data (based on nuclear magnetic resonance and specific analysis of plant- and microbial-derived compounds) to better understand how ecosystem properties control soil C biogeochemistry and dynamics. Doubled aboveground litter additions did not increase soil C for any of the forests studied likely due to long-term soil priming. The degree of SOM decomposition was higher for bacteria-dominated sites with higher nitrogen (N) availability while lower for the N-poor coniferous forest. Litter exclusions significantly decreased soil C, increased SOM decomposition state, and led to the adaptation of the microbial communities to changes in available substrates. Finally, although aboveground litter determined soil C dynamics and its molecular composition in the coniferous forest (HJA), belowground litter appeared to be more influential in broadleaf deciduous forests (BH and HF). This synthesis demonstrates that inherent ecosystem properties regulate how soil C dynamics change with litter manipulations at the molecular-level. Across the forests studied, 20 years of litter additions did not enhance soil C content, whereas litter reductions negatively impacted soil C concentrations. These results indicate that soil C biogeochemistry at these temperate forests is highly sensitive to changes in litter deposition, which are a product of environmental change drivers.

Spectroscopic and Molecular Characterization of Water Soluble Organic Matter from Sediments in the Macrophyte-dominated and Algae-dominated Zones of Taihu Lake

Macrophyte- and algae-dominated lakes (zones) are the two typical states of shallow lakes, where the source and composition of organic matter are distinct. The burial of organic matter (OM) in the sediment supports the role of lakes as carbon sinks. However, organic matter in the sediments could be further processed, influencing the carbon cycle. The post-burial metabolism of the sedimentary OM relates closely to its composition. However, information on the differences in composition remains limited, especially the molecular composition of organic matter from sediments in the macrophyte-dominated and algae-dominated lakes. In this study, sediments were collected from the macrophyte-dominated and algae-dominated zones of Taihu Lake (East Taihu Lake and Meiliang Bay, respectively), and the active pool of sedimentary OM (water soluble organic matter, WSOM) was extracted and purified. The composition of the WSOM was characterized in detail via absorption spectroscopy, fluorescent spectroscopy, infrared spectroscopy, and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). The optical index of E2:E3 showed that the molecular size of WSOM in the macrophyte-dominated zone (M-WSOM) was slightly larger than that in the algae-dominated zone (A-WSOM). Consistently, the intensity-weighted molecular weights were identified as 388.9 and 379.9, respectively, via FT-ICR MS analysis. M-WSOM was more humified than A-WSOM, as evidenced by the SUVA254 and HIX values. The FT-ICR MS results showed that the relative abundance of the condensed aromatic substance and the aromatics were 6.3% (intensity-weighted) and 7.7% for M-WSOM and 1.1% and 4.4% for A-WSOM, respectively. The excitation-emission matrix fluorescence-parallel factor analysis (EEM-PARAFAC) suggested that the protein-like component was more in A-WSOM than that in M-WSOM, and the FT-ICR MS results showed that the intensity-weighted relative abundances of peptides were 35.6% and 15.6% for A-WSOM and M-WSOM, respectively. The FT-ICR MS results further showed that the heteroatom-containing molecules were abundant in the sedimentary WSOM, i.e., 82.9% and 91.7% for M-WSOM and A-WSOM, respectively. The nitrogen-containing molecules dominated, contributing to 53.5% and 78.5% of M-WSOM and A-WSOM, respectively. There were 30.4% and 41.4% phosphorus-containing molecules in M-WSOM and A-WSOM, respectively. The phosphorus-containing molecules in M-WSOM were mainly aliphatics and highly unsaturated structures with low oxygen, whereas those in A-WSOM were mainly peptides. This study elucidated the detailed molecular composition of WSOM in the macrophyte-dominated and algae-dominated zones of Taihu Lake, which aids understanding of the carbon, nitrogen, and phosphorus biogeochemical cycles in lakes.

Study of the molecular-structural composition of alcoholic extracts of radio-induced potato tubers by mass spectrometry and EPR

This article presents data on electron paramagnetic resonance (EPR) and mass spectrometric analysis of potato tubers, irradiated with gamma rays, in order to examine and identify changes in the molecular composition of organic matter following radiation exposure. The products of the Maillard reaction were compared with the products of intramolecular radiolysis of organic constituents of potatoes. The presence of free radicals was verified using EPR. DDPM (2,3-dihydro-3,5-dihydroxy-6-methyl-4 (H) -pyran-4-one) was among the radiolysis products detected via mass spectrometry, which points to the intramolecular dehydration of potato carbohydrates. EPR signals indicate single-electron transitions of the semidione radical anionic molecular compounds. It has been shown that irradiation with gamma rays significantly destroys the carbohydrate, lipid, keto-carotene and amino acid molecules of potatoes.

Tillage management exerts stronger controls on soil microbial community structure and organic matter molecular composition than N fertilization

Different tillage and nitrogen (N) fertilization practices markedly alter soil carbon dynamics, yet the underlying mechanisms and their interactive controls on soil organic matter (OM) biogeochemistry are still not well defined. Soil samples were collected from a 24-year field trial comprising of two tillage practices (conventional and conservation) and two N fertilization rates (low: 12, moderate: 132–172 kg N ha-1 yr-1) in Southern Ontario, Canada. Soil organic carbon, molecular-level OM characterization using targeted compound and solid-state 13C nuclear magnetic resonance (NMR) analyses, bacterial and fungal abundance using quantitative PCR and community composition using DNA sequencing were used to assess differences in soil carbon processes. Despite similar soil organic carbon concentrations across treatments (16.7–31.2 g/kg), conservation tillage increased specific OM components (i.e., long-chain acyclic lipids, cyclic lipids and simple sugars) than conventional tillage for both N rates. Cutin- and suberin-derived compounds were also higher under conservation than conventional tillage with both N levels, suggesting the preservation of cutin- and suberin-derived compounds with conservation tillage. In contrast, conservation tillage resulted in lower lignin-derived compounds relative to conventional tillage for both N rates (5.4–5.8 vs. 6.3–9.6 mg/g soil OC), likely due to higher decomposition of lignin associated with altered microbial community composition. Under conventional tillage, moderate N fertilization resulted in lower lignin-derived compounds than low N addition (6.3 vs. 9.6 mg/g soil OC). Interestingly, the significant differences between the two N rates for several soil OM compounds and fungal community composition were only observed with conventional tillage but not conservation tillage, suggesting that the control of N fertilization on soil OM dynamics may depend on the type of tillage practices. Overall, tillage management is a more important driver of soil carbon cycling than N fertilization, and conservation tillage may enhance the decomposition of specific soil OM components (i.e., lignin-derived compounds) via changes in microbial communities.

Twenty years of litter manipulation reveals that above-ground litter quantity and quality controls soil organic matter molecular composition

Twenty years of litter manipulation reveals that above-ground litter quantity and quality controls soil organic matter molecular composition

Spatial and Temporal Variability of Dissolved Organic Matter Molecular Composition in a Stratified Eutrophic Lake

AbstractDissolved organic matter (DOM) is an intermediate between organic carbon formed by primary producers and carbon dioxide (CO2) produced through respiration, making it a key component of the carbon cycle in aquatic ecosystems. Its composition influences the routes of mineralization. Here, we evaluate DOM composition as a function of time and depth in Lake Mendota, a highly productive eutrophic lake that stratifies in warm months and is located in Madison, Wisconsin, USA. Dissolved organic carbon concentrations and optical properties are presented for 73 samples collected at a single location at varying depths within the water column from June to November. A subset of samples is analyzed by Fourier transform‐ion cyclotron resonance mass spectrometry (FT‐ICR MS) to investigate DOM composition at the molecular level. Temporally, increases in more oxidized formulas are observed in both the epilimnion and hypolimnion. At the surface, correlations between DOM formulas and both chlorophyll concentrations and light intensity show that photochemical reactions contribute to DOM oxidation. In the hypolimnion, redox conditions and interactions with sediments likely influence temporal compositional change. Our results show DOM composition varies with depth with more highly oxidized formulas identified deeper in the water column. However, DOM composition varies more temporally than by location within the water column. This work has implications for climate change as DOM photooxidation in lakes represents an understudied flux of CO2 to the atmosphere. Additionally, lake eutrophication is increasing due to warming temperatures and this data set yields detailed molecular information about DOM composition and processing in such lakes.

Warming and elevated CO2 promote rapid incorporation and degradation of plant-derived organic matter in an ombrotrophic peatland.

Rising temperatures have the potential to directly affect carbon cycling in peatlands by enhancing organic matter (OM) decomposition, contributing to the release of CO2 and CH4 to the atmosphere. In turn, increasing atmospheric CO2 concentration may stimulate photosynthesis, potentially increasing plant litter inputs belowground and transferring carbon from the atmosphere into terrestrial ecosystems. Key questions remain about the magnitude and rate of these interacting and opposing environmental change drivers. Here, we assess the incorporation and degradation of plant‐ and microbe‐derived OM in an ombrotrophic peatland after 4 years of whole‐ecosystem warming (+0, +2.25, +4.5, +6.75 and +9°C) and two years of elevated CO2 manipulation (500 ppm above ambient). We show that OM molecular composition was substantially altered in the aerobic acrotelm, highlighting the sensitivity of acrotelm carbon to rising temperatures and atmospheric CO2 concentration. While warming accelerated OM decomposition under ambient CO2, new carbon incorporation into peat increased in warming × elevated CO2 treatments for both plant‐ and microbe‐derived OM. Using the isotopic signature of the applied CO2 enrichment as a label for recently photosynthesized OM, our data demonstrate that new plant inputs have been rapidly incorporated into peat carbon. Our results suggest that under current hydrological conditions, rising temperatures and atmospheric CO2 levels will likely offset each other in boreal peatlands.

Dynamics of organic matter molecular composition under aerobic decomposition and their response to the nitrogen addition in grassland soils

Grassland soils store a substantial proportion of the global soil carbon (C) stock. The transformation of C in grassland soils with respect to chemical composition and persistence strongly regulate the predicted terrestrial-atmosphere C flux in global C biogeochemical cycling models. In addition, increasing atmospheric nitrogen (N) deposition alters C chemistry in grassland soils. However, there remains controversy about the importance of mineralogical versus biochemical preservation of soil C, as well as uncertainty regarding how grassland soil C chemistry responds to elevated N. This study used grassland soils with diverse soil organic matter (SOM) chemistries in an 8-month aerobic incubation experiment to evaluate whether the chemical composition of SOM converged across sites over time, and how SOM persistence responded to the N addition. This study demonstrates that over the course of incubation, the richness of labile compounds decreased in soils with less ferrihydrite content, whereas labile compounds were more persistent in ferrihydrite rich soils. In contrast, we found that the richness of more complex compounds increased over the incubation in most sites, independent of soil mineralogy. Moreover, we demonstrate the extent to which the diverse chemical composition of SOM converged among sites in response to microbial decomposition. N fertilization decreased soil respiration and inhibited the convergence of molecular composition across ecosystems by altering N demand for microbial metabolism and chemical interactions between minerals and organic molecules. This study provides original evidence that the decomposition and metabolism of labile organic molecules were largely regulated by soil mineralogy (physicochemical preservation), while the metabolism of more complex organic molecules was controlled by substrate complexity (biochemical preservation) independent to mineral-organic interactions. This study advanced our understanding of the dynamic biogeochemical cycling of C by unveiling that N addition dampened C respiration and diminished the convergence of SOM chemistry across diverse grassland ecosystems.

Use of Thermally Assisted Hydrolysis and Methylation (THM-GC-MS) to Unravel Influence of Pottery Production and Post-Depositional Processes on the Molecular Composition of Organic Matter in Sherds from a Complex Coastal Settlement

Ceramic fragments from the Islet of Guidoiro Areoso (NW Spain), covering a wide range of cultural periods (Neolithic to Late Bronze Age), have been studied by color analysis, elemental analysis of carbon (C) and nitrogen (N), and molecular analysis (thermally assisted hydrolysis and methylation, THM-GC-MS), in order to identify the organic matter (OM) in the prehistoric pottery and reveal information on ceramic production techniques, food remains and post-depositional effects. Results showed that the strong marine influence (sherds recovered from coastal deposits) and microbial activity (recovery from waste deposits, “cuncheiros”) had a profound effect on C/N ratio and molecular composition (N-rich protein and chitin structures). Other organic ingredients originated from the material used for creating the ware (detected as pyrogenic OM) and possibly food remains (fatty acid fingerprints). Dark-colored ware was enriched in both pyrogenic OM from incomplete combustion and non-bacterial fatty acids. Fatty acid patterns could not be related to possible vessel use, and markers of aquatic resources were scarce, or absent. It is argued that THM-GC-MS of pottery fragments is useful for understanding how an archaeological deposit developed in time, what kinds of OM are present, and possibly to make a pre-selection of samples with high potential for more cost-demanding dietary molecular assessments.

9000 years of changes in peat organic matter composition in Store Mosse (Sweden) traced using FTIR‐ATR

Store Mosse (the ‘Great Bog’ in Swedish) is one of the most extensive bog complexes in southern Sweden (~77 km2), where pioneering palaeoenvironmental research has been carried out since the early 20th century. This includes, for example, vegetation changes, carbon and nitrogen dynamics, peat decomposition, atmospheric metal pollution, mineral dust deposition, dendrochronology, and tephrochronology. Even though organic matter (OM) represents the bulk of the peat mass and its compositional change has the potential to provide crucial ecological information on bog responses to environmental factors, peat OM molecular composition has not been addressed in detail. Here, a 568‐cm‐deep peat sequence was studied at high resolution, by attenuated reflectance Fourier‐transform infrared spectroscopy (FTIR‐ATR) in the mid‐infrared region (4000–400 cm–1). Principal components analysis was performed on selected absorbances and change‐point modelling was applied to the records to determine the timing of changes. Four components accounted for peat composition: (i) depletion/accumulation of labile (i.e. carbohydrates) and recalcitrant (i.e. lignin and other aromatics, aliphatics, organic acids and some N compounds) compounds, due to peat decomposition; (ii) variations in N compounds and carbohydrates; (iii) residual variation of lignin and organic acids; and (iv) residual variation of aliphatic structures. Peat decomposition showed two main patterns: a long‐term trend highly correlated to peat age (r = 0.87), and a short‐term trend, which showed five main phases of increased decomposition (at ~8.4–8.1, ~7.0–5.6, ~3.5–3.1, ~2.7–2.1 and ~1.6–1.3 ka) – mostly corresponding to drier climate and its effect on bog hydrology. The high peat accumulation event (~5.6–3.9 ka), described in earlier studies, is characterized by the lowest degree of peat decomposition of the whole record. Given that FTIR‐ATR is a quick, non‐destructive, cost‐effective technique, our results indicate that it can be applied in a systematic way (including multicore studies) to peat research and provide relevant information on the evolution of peatlands.

Conservation tillage for 17 years alters the molecular composition of organic matter in soil profile

Conservation tillage is considered as a potential measure to mitigate climate change by sequestering soil organic matter (SOM), however its stabilization mechanisms remain elusive. In this study, we revealed the molecular composition of SOM in soil profile (~50 cm depth) from a 17-yr tillage experiment in North China. The soils were collected from 0–10, 10–20, 20–30 and 30–50 cm layers under conventional tillage (CT), and conservation tillage such as rotary tillage (RT) and no-tillage (NT). The sequential solvent extraction and CuO oxidation methods were used to quantify free lipids and lignin-derived phenols. The results showed that NT (cf. CT) increased labile compounds (i.e., carbohydrates) and plant-derived SOM (i.e., long-chain (≥C20) aliphatic lipids and steroids) in the 0–10 and 30–50 cm layers. The RT (cf. CT) increased the total free lipids by 72–133% in the sublayers (>10 cm). The RT (cf. CT and NT) resulted in higher preservation of plant-derived (≥C20 aliphatic lipids and steroids) and microbial-derived compounds (<C20 aliphatic lipids and trehalose) SOM in deep soils (i.e., ≥10 cm). Conservation tillage suppressed lignin degradation, as reflected by 32–137% higher total lignin-derived phenols under RT and NT than CT in the 0–10 and 30–50 cm layers. The NMR revealed higher aliphatic to aromatic C ratio under NT and RT in the whole soil profile, suggesting more aliphatic lipids accumulated. Conservation tillage increased SOC stocks by 10–14% in 0–10 cm layer but not in deeper profiles. These results suggest that conservation tillage have increased plant-derived lipids and lignin accumulation. Our study highlights that conservation tillage (particularly the RT) after 17 years alters SOM molecular compositions and degradation processes in the soil profile. These findings have implications for improving our understanding of C stabilization mechanisms in agroecosystems.

Hydrocarbon Generation and Chemical Structure Evolution from Confined Pyrolysis of Bituminous Coal.

The molecular composition of organic matter formed during pyrolysis is complex. Fourier transform infrared spectroscopy (FTIR) is a good technique to investigate the coal chemical structural evolution. However, reports on the effects of chemical structure on the n-alkane yields and their relative functional groups are scarce in the literature. In our case, the chemical structural evolution process of bituminous coal obtained by pyrolysis at two different heating rates has been analyzed by pyrolysis-gas chromatography (Py-GC) and FTIR. Furthermore, some of the small molecular compounds (e.g., n-alkanes 24 can generate n-alkanes 20 or low-weight compounds) generated by gold-tube pyrolysis were identified using other GC techniques. Biomarkers were analyzed and compared to generated n-alkanes from the gold-tube pyrolysis experiments. We present the results of the relationship between the FTIR parameters and the molecular compositions that were analyzed. A good linear relationship can be seen between the FTIR parameters (C=O, C=C, and C-factor values), the carbon preference index (CPI), and the ratio of the pristane content and n-C17 alkane content (Pr/n-C17). Furthermore, the n-alkane fraction of the pyrolysates, in particular pristane, phytane, n-C17 alkane, and n-C18 alkane, changed upon maturation. Our conclusions indicate that FTIR is applicable as a structural and chemical change probe to explore the pyrolysis process.