Characterization Of Organic Matter Research Articles

Application of Optical-electron Correlative Microscopy for Characterization of Organic Matter

ABSTRACT Application of coal petrology is known to play significant role in several industrial sectors viz. thermal industries, steel industries, unconventional oil and gas fields. One important aspect of organic matter characterization, especially for unconventional oil and gas fields is the development of organic matter hosted porosity, and commonly Scanning Electron Microscopy (SEM) is used to study the same. While, SEM helps in understanding the nature of porosity developed in coals and shales, one significant limitation is that under SEM the different organic matter types can’t be distinguished, as all organic matter appears dark due to their lower atomic mass. Optical-electron correlative microscopy has recently gained importance for making advancement in addressing the abovementioned scientific gap. While this method has been found some usage for characterizing the dispersed organic matter in shales, only one work globally exists where the technique has been used for studying coals. In this work, possibly, for the first time, this technique is applied for characterizing three Indian coals from Korba basin, India, with the main objective of establishing necessary protocols for reliable imaging of different organic matter types under SEM. Our results establish that imaging under SEM using Backscattered electron (BSE) detector, the macerals and mineral matter were clearly discernible at 15 kV accelerating voltage. Further, this exercise also indicates that identification of vitrinite macerals under SEM, without correlative technique can be challenging, while some inertinites with their distinctive structures can be identified under stand-alone SEM. Sporinites too, due to their distinctive morphology, were easily identifiable under SEM.

Impact of dissolved organic matter characteristics and inorganic species on the stability and removal by coagulation of nanoplastics in aqueous media

The aggregation of rough, raspberry-type polystyrene nanoparticles (PS-NPs) was investigated in the presence of six hydrophobic and hydrophilic dissolved organic matter (DOM) isolates and biopolymers (effluent OM) in NaCl and CaCl2 solutions using time-resolved dynamic light scattering. Results showed that the stability of PS-NPs mainly depends on OM characteristics and ionic composition. Due to cation bridging, the aggregation rate of PS-NPs in Ca2+-containing solutions was significantly higher than at similar Na+-ionic strength. Biopolymers rich in protein and carbohydrate moieties showed higher affinity to the surface of PS-NPs than the other DOM isolates in the absence of both Ca2+ and Na+. Overall, the stability of PS-NPs followed the order of biopolymers > hydrophobic isolates > hydrophilic isolates in the presence of Na+ and biopolymers > hydrophilic isolates > hydrophobic isolates in Ca2+-containing solutions. In the presence of high MW structures (biopolymers), PS-NPs aggregation in both NaCl and CaCl2 solutions was attributed to steric repulsive forces. The impact of hydrophilic and hydrophobic isolates on PS-NPs aggregation highly relied on the ionic composition. Coagulation was an effective pretreatment for PS-NPs removal. Using inductively coupled plasma-mass spectrometry, higher removals were recorded with Al2(SO4)3 in the absence of DOM, while PACl more efficiently coagulated PS-NPs in the presence of DOM isolates.

Study on Grain Size, Physical Properties and Organic Matter Characteristics of Tidal Flat Surface Sediments: May 2022 Hwangdo Tidal Flat Dataset, Cheonsu Bay

This study analyzes the geological and geochemical features of surface sediments in the Hwangdo Tidal Flat, located on Korea’s West Coast. The tidal flat experiences semi-diurnal tides, impacting organic matter decomposition and nutrient cycling. Ninety one sediment samples were collected and analyzed for physical and chemical properties including grain size, density, water content, organic carbon, and nitrogen. Sediments consist mainly of sand and silt, with coarser sediments near the main channel and finer sediments towards the west. Sediment grain size averages 4.12 Φ with a sorting coefficient of 1.96 Φ, indicating diverse energy environments. Total organic carbon and nitrogen correlate positively with grain size and density, reflecting sediment origin and environment. Kriging maps sediment grain size distribution, while correlation and linear regression analyses show relationships between variables. High correlations exist between various parameters, aligning with tidal flat characteristics and aiding understanding of sediment transport and deposition. The study provides baseline data for understanding the tidal flat’s geological, geochemical, and physical aspects, valuable for remote sensing validation and environmental monitoring. The dataset is freely available for research and management purposes.

Evaluation of the biodegradability of hazardous industrial solid waste: Study of key parameters.

The biological stability of solid waste is one of the main problems related to the environmental impact of landfills and their long-term emission potential. Current European legislation (European Landfill Directive, EC/99/31) introduced the need to reduce biodegradable organic compounds deposited in landfills; however, it set neither official parameters nor methods to define the stability of such a waste. In Spain, biodegradability is generally evaluated using the biological oxygen demand/chemical oxygen demand (BOD5/COD) ratio, measuring it on the leachate, thus not considering the non-soluble fraction and therefore creating false negatives. To solve this problem, the biodegradability of hazardous industrial waste has been determined by measuring its respirometric activity (AT4). Our results show that the measure of the AT4 is independent of the enrichment with a microbial inoculum, and a sample size no higher than 20g could be a reasonable value for a sensitive biodegradability determination. The highest respirometric index is obtained in waste with pH values between 6.5 and 10.5. Furthermore, respirometric biodegradability values are independent of traditional parameters of organic matter characterization such as BOD5/COD ratio, volatile content, and total and dissolved organic carbon. Consequently, the AT4 parameter provides new information on the composition and stability of organic matter in hazardous industrial waste. Its incorporation into pre-disposal waste characterization protocols allows to identify waste that exceeds recommended biodegradability thresholds. This approach ensures that only waste meeting specified biodegradability standards is deposited, avoiding landfill emissions and related environmental impacts, and thereby improving the overall effectiveness and sustainability of waste management practices.

Divergent response of Chernozem organic matter towards short-term water stress in Poa pratensis L. rhizosphere and bulk soil in pot experiments: A spectroscopic study

Understanding and controlling rhizospheric processes under abiotic stress is one of the key challenges in addressing food security amid the climate crisis. In this work, the impact of short-term drought and overwatering on soil organic matter (SOM) of Haplic Chernozem in the rhizosphere of Poa pratensis L. and in bulk soil was investigated. The vegetation experiment was conducted in a climatic chamber at soil moisture levels of 35, 80, and 200 % of the field capacity. UV-Vis and spectrofluorometry were used to describe the water-extractable organic matter (WEOM) characteristics and fluorofores signature, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to describe functional group composition of SOM. Composition and properties of SOM and WEOM of Chernozem significantly change after exposure to short-term water stress. Drought does not affect the composition of rhizosphere SOM except increasing the proportion of polysaccharides, but leads to the decrease in aromaticity and increase in molecular weight of humic-like components of rhizosphere WEOM. These findings reflect Poa adaptation to water deficiency and microbial activity suppression which results in accumulation of SOM intermediate decomposition products. On the contrary, bulk WEOM wasn't affected by drought but SOM became enriched with aromatic and oxidised components. Overwatering leads to equalisation of bulk and rhizospheric SOM composition due to a decrease in the proportion of aromatic and carboxylic components of bulk SOM and the accumulation of microbial products in both bulk and rhizospheric SOM. In general, rhizospheric WEOM undergoes relatively significant changes relative to the optimum water regime under moisture deficit, and bulk WEOM — under overwatering. The findings illustrate the involvement of the both WEOM and SOM in maintaining resilience of the soil-plant system as well as the difference in watering conditions impact on SOM in rhizosphere and bulk soil. SOM spectral data can be used for assessing the state of soil systems, such as changes in microbial activity and adaptation of the soil-plant system to abiotic stress. Our findings also illustrate the differences in the organic matter transformation of the Poa pratensis rhizosphere and the bulk Chernozem depending on environmental factors.

Characteristics of organic matter driven by Eichhornia crassipes during co-contamination with per(poly)fluoroalkyl substances (PFASs) and microplastics (MPs)

Co-contamination with MPs and PFASs has been recorded, particularly in surface-water environments. Floating macrophyte microcosms are an important part of the surface water ecosystem, and dissolved organic matter (DOM) driven by floating macrophytes (FMDDOM) is critical for maintaining material circulation. However, knowledge gaps remain regarding the impact of MPs and PFASs co-pollution on FMDDOM. An greenhouse simulation experiment was conducted in this study to investigate the effects of four PFASs, perfluorooctanoic acid (PFOA), perfluoro-octane-sulfonic acid (PFOS), perfluoro-2-methyl-3-oxahexanoic acid (Gen X), and potassium 9-chlorohexadecafluoro-3-oxanonane-1-sulfonate (F-53B), on FMDDOM sourced from Eichhornia crassipes (E. crassipes), a typical floating macrophyte, in the presence and absence of polystyrene (PS) MPs. Four PFASs increased FMDDOM release from E. crassipes, leading to a 32.52–77.49 % increase in dissolved organic carbon (DOC) levels. PS MPs further increased this, with results ranging from −21.28 % to 26.49 %. Based on the parallel factor analysis (PARAFAC), FMDDOM was classified into three types of fluorescent components: tryptophan-like, humic-like, and tyrosine-like compounds. Contaminants of MPs and PFASs modified the relative abundance of these three components. Protein secondary structure analysis showed that fluorocarbon bonds tended to accumulate on the α-helix of proteins in FMDDOM. The relative abundance of fluorescent and chromophorous FMDDOMs varied from 0.648 ± 0.044 to 0.964 ± 0.173, indicating that the photochemical structures of the FMDDOM were modified. FMDDOM exhibits decreased humification and increased aromaticity when contaminated with MPs and PFASs, which may be detrimental to the geochemical cycling of carbon. This study offers a theoretical basis for assessing the combined ecological risks of MPs and PFASs in floating macrophyte ecosystems.

Analysis of dissolved organic matter characteristics in pharmaceutical wastewater via spectroscopy combined with Fourier-transform ion cyclotron resonance mass spectrometry

Studying the changes in organic matter and characteristic pollutants during the treatment of penicillin-containing pharmaceutical wastewater, which can be reflected by changes in dissolved organic matter (DOM), is crucial for improving the effectiveness of wastewater treatment units and systems. Herein, water quality indicators, spectroscopic methods, and Fourier-transform ion cyclotron resonance mass spectrometry were utilized to characterize the general molecular compositions and specific molecular changes in DOM during the treatment of typical penicillin-containing pharmaceutical wastewater, including in each of the influent, physicochemical treatment, biological treatment, oxidation treatment, and effluent stages. The influent exhibited a high organic matter content (concentration of dissolved organic carbon >10,000 mg·L−1), its DOM mainly contained protein- and lignin-like substances composed of CHON and CHONS molecules, and the relative intensity (RI) of penicillin was extremely high (RI = 0.220). Compared with the influent, the abundance of CHON and CHONS molecules detected after physicochemical treatment decreased by 70.3 % and 62.5 %, respectively, and the RI of penicillin decreased by 85.5 %. Biological treatment caused substantial changes in DOM components through oxidation, dealkylation, and denitrification reactions, accounting for 36.8 %, 28.9 %, and 14.8 % of the total identified reactions, respectively. Additionally, lignin-like substances were generated in large quantities, the overall humification level significantly increased, and the RI value increased for the penicillin intermediate, 6-aminopenicillanic acid (6-APA). Oxidation treatment effectively removed phosphorus-containing substances and some lignin-like substances produced by biological treatment; however, it was not effective in removing characteristic pollutants such as 6-APA. Such characteristic substances continued to be present in the effluent, and the DOM mainly contained protein- and humus-like substances, accounting for 30.8 % and 47.3 %, respectively. The study findings reveal the changes in organic matter and characteristic pollutants during the treatment of penicillin-containing wastewater from the perspective of the general molecular composition and specific molecular changes in DOM, providing support for further exploration of wastewater treatment mechanisms and improvements in treatment unit efficiency.

Influences of wildfire on the soil dissolved organic matter characteristics and its electron-donating capacity

Global increases in the intensity and frequency of wildfires are driving major changes in soil organic matter (SOM) characteristics, including soil dissolved organic matter (DOM). As the most crucial component of SOM, soil DOM plays a pivotal role in the carbon cycle and regulates the environmental fate of contaminants through its versatile reactivities, including electron-donating capacity (EDC). However, it is still being determined how wildfire influences key characteristics of soil DOM and subsequent effects on EDC in forest soils. Thus, we conducted our study to fill this gap with the forest soils of Jinyun Mountain Nature Reserve of China, which experienced an unprecedented wildfire event in 2022. The results from optical characterization, high-performance size-exclusion chromatography (HPSEC), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) showed decreasing molecular weight but elevating nitrogen-containing molecular formulas of soil DOM in the burned soils. This could be attributed to the Maillard reaction and microbial re-colonies. Additionally, wildfires increased the condensed aromatics and lignin components in soil DOM. In the burned soils, we observed increasing EDC of soil DOM, which accounts for an increase in lignin-derived phenolic components. Overall, the findings of this study demonstrate that eco-disturbances, such as wildfires, induce alterations in the properties of DOM, leading to variations in its reactivity and potentially influencing the fate of environmental pollutants beyond carbon dynamics alone. Thus, incorporating the dynamic properties of soil DOM, particularly in the context of climate change, can enhance the assessment of risks associated with contaminants in soil and water, providing valuable insights.

Characterization of sediment organic matter in the outer Yangtze River Estuary using stable isotopes, optical techniques, and FT-ICR-MS: Implications for the carbon burial mechanism

The burial of sediment organic matter (SOM) in the estuary and shelf plays an important role in the global carbon cycle. However, it is challenging to determine the source, composition, and burial of SOM in the coastal sea, especially at the molecular level. This was explored in the coastal area outside the largest Yangtze River of China with multiple techniques including elemental and stable isotopic analysis, absorption spectroscopy, fluorescence excitation-emission matrices coupled with parallel factor analysis (EEMs-PARAFAC), and ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The end-member mixing analysis based on δ13C and δ15N showed a dominance of marine contribution (up to 70%) at most stations while the terrestrial contribution increased to >55% nearshore in summer at a high fluvial sediment flux. This was consistent with the offshore decreasing humic-like C1 and C2, humification index (HIX), %lignin-like compounds, and %CHO but increasing tryptophan-like C3, biological index (BIX), %protein-like compounds, and %CHOS from EEMs-PARAFAC and FT-ICR-MS analysis. The %clay correlated positively with SOM content, HIX, %lignin-like compounds, O/C, and modified aromaticity index (AImod) but correlated negatively with %C3, H/C, and the relative abundance of labile formulas (MLBL), while %silt showed contrasting correlations. These results indicated the fine clay sediments adsorbed more humified, aromatic, oxygenated, and terrestrial compounds that were probably more resistant to biodegradation and thus had a higher burial efficiency than those on the silty sediments. Principal component analysis based on SOM indices further revealed different characteristics of SOM in the nearshore, northern offshore, and southern offshore regions, which were probably dependent on the delivery by local current systems. Overall, these findings contributed to unraveling the source and molecular composition of SOM associated with different grain size sediments and local current delivery, which are fundamental for understanding the factors underlying carbon burial in the complex coastal environment.

Tracing fluorescent dissolved organic matter (fDOM) characteristics and water quality parameters: Insights from an urban industrial river to marine zone.

This study aims to identify continuous water quality changes and identify fluorescence properties from urban rivers to marine zones. Various types of natural and anthropogenic sources derived dissolved organic matter (DOM) have been identified in this study. These include soil-derived DOM, plant remnants, and soluble particles produced when organic material partially decomposes and is released by microorganisms, such as bacteria, algae, and plants. DOM was characterized using a three-dimensional excitation-emission matrix (3DEEM), parallel factor analysis (PARAFAC), and water quality parameters from the Buriganga River, Dhaka to Patenga Seaport, Chittagong, along with the Shitalakshya River, a small portion of the Padma River, and the Meghna River. To better understand the data analysis, the study area was divided into three central regions: urban industrial rivers, industrial estuarine rivers, and marine zones. In the urban industrial river, 3DEEM and PARAFAC identified five fluorophores (peaks: A, C, M, T, and Tuv) with five components: detergent-like, fulvic-like, tryptophan or protein-like, fulvic-like (C-type), and protein-like, which might originate from the industrial activities and sewage pollution. In the industrial estuarine river zone, three fluorophores have been identified (peaks: A, C, Tuv) with two known components, namely, fulvic acid (A-type) and fulvic acid (C-type), with an unknown photoproduct at Ex/Em = 295/368 (peak Tuv). Components in the industrial river zone may originate from terrestrial sources, indicating vegetation along the river. In the marine zone, four fluorophores have been identified (peaks: Tuv, A, T, C) with two components, that is, protein- or tryptophan-like and humic acid-like from coral origin. The intensities of both fulvic-like and protein-like substances were high in urban industrial river water owing to industrial activity and sewage pollution. SUVA254 suggests high aromaticity in all three regions, whereas the optical properties suggest that terrestrial and microbial components are present in the urban industrial and estuarine rivers. This further indicates that urban industrial river water quality is highly polluted. The lowest degradation potential index (DPI) in the marine zone might result from the presence of the highest number of dissolved solids in the water, and the highest DPI of industrial estuarine rivers explains the comparatively high presence of terrestrial-derived humic (A)- and humic (C)-like components in the ratio to the unknown photoproduct of mid-wavelength. PRACTITIONER POINTS: This study's uniqueness is a 220-km cruise from an urban river to a coastal seaport to analyze fluorescence properties. The study found that most water parameters were within the DoE standards, except for DO, which was consistently low. 3DEEM-PARAFAC identified five fluorophores linked to detergent, fulvic, and protein-like substances from sewage and industrial sources. Our study concludes that microbial and terrestrial sources dominate dissolved organic matter in urban, estuarine, and marine regions.

Depositional environments and thermal maturity of the hydrocarbon source rocks in the Devonian–Early carboniferous Ora Formation from palynological organic petrographic investigations in northern and western Iraq

The study investigates the palynofacies, organic matter character, and hydrocarbon generation potential of this rock unit, based on surface and subsurface samples from the Ora Formation type-section in extreme northern Iraq and the Akkas-3 well in western Iraq, respectively. Dark, mostly oxidized, gelified platy amorphous organic matter (AOM) dominates the palynological components in the surface section, in addition to a few rounded spores and structured phytoclasts. In contrast, palynomorphs, including Ambitisporites avitus, Aneurospora spp., Vallatisporites verrucosus, Acinosporites spp., Verrucosisporites nitidus and the algae Botryococcus, are predominant in studied samples from the Akkas-3 well. Statistical cluster analysis identified three palynofacies types in the surface section based on stratigraphic variations in the particulate organic matter. These vary from high amorphous organic matter (AOM), moderate phytoclast, and low palynomorph abundances that represent proximal suboxic–anoxic shelfal environments to moderate to good AOM and low to moderate palynomorph abundances that represent distal suboxic–anoxic or distal dysoxic–anoxic shelfal environments. The organic petrographic study of the outcrop section also revealed the strong effect of oxidation, where dispersed terrigenous and amorphous organic materials in the form of granular and gelified forms dominate and reflect a terrestrial origin of these components. In the subsurface section, a mixed terrestrial and less marine or lacustrine origin characterized the studied organic matter, where land plant spores (sporinite), in addition to vitrinite and inertinite, are dominant with a few scattered liptinite macerals. The difference in thermal maturity between the outcrop and subsurface samples is likely due to the higher tectonic burial of the outcrop samples that form part of the Northern Thrust Zone of Iraq. Nevertheless, higher abundances of AOM (oil-prone kerogen type II) accumulated in the northern outcrop type section. This might imply that the Ora Formation has a higher potential for hydrocarbon production north of the Akkas field.

Organic Matter Enrichment in Jurassic Hydrocarbon Source Rocks from the Turpan-Hami Basin: Insights from Organic and Elemental Geochemistry.

Petroleum can be generated by thermal cracking of organic matter within sediments, and the organic matter within sediments plays the dominant role in determining oil and gas generation. Organic matter within sediments is characterized by various sources, such as sapropelic organic matter from algal, microbial, and planktonic organisms and humic organic matter from higher plants. Paleo-productivity, terrestrial influx, and depositional environments could obviously influence the enrichment processes of the organic matter within sediments. Organic and elemental geochemical proxies can investigate the sedimentary process and reflect the enrichment characteristics of organic matter. In this study, hydrocarbon source rocks from the Shuixigou Group were collected from the Taibei Sag of the Turpan-Hami Basin, rock-eval pyrolysis was conducted, and stable carbon isotope composition of organic carbon and major and trace element distributions were measured. Based on this, the type and maturation of organic matter, paleo-productivity, terrestrial influx, and depositional paleo-environments were investigated. The results show that the Jurassic hydrocarbon source rocks are characterized by type III kerogen and are in the oil-window stage of maturation. The depositional paleo-environments of hydrocarbon source rocks in different formations are not remarkably different. The water bodies have freshwater oxidizing environments, and the paleo-climatic characteristics are warm and humid. However, the paleo-productivity of samples from the lower Jurassic Sangonghe Formation is higher than samples from other formations. Overall, the organic matter enrichment in Jurassic hydrocarbon source rocks of the Turpan-Hami Basin could be mutually controlled by the paleo-productivity and depositional paleo-environments. The results of this study could provide theoretical insight into deep petroleum exploration and resource evaluation in the Turpan-Hami Basin.

Molecular Structural Characteristics and 3D Model Reconstruction of Organic Matter in Longmaxi Formation Shale.

The establishment of molecular structure modeling is an important means to study the pore characteristics of shale organic matter and is significant for molecular-level simulations of gas storage and diffusion. Using 13C NMR, FTIR, and XPS combined with the split-peak fitting technique, the structural characteristics of the aromatic structure, aliphatic structure, and oxygen functional groups of kerogen from the shale of the Longmaxi Formation, Wuxi County, Chongqing Municipality, were quantitatively characterized. A macromolecular structure model of the kerogen was also constructed by using the 2D macromolecular structure model construction method in combination with elemental analysis experiments. The results showed that the 2D single-molecule structural model of the sample consisted of 2 benzenes, 2 naphthalenes, 1 anthracene, 5 pyrenes, 1 pyridine, and 1 pyrrole. The C skeleton types were 93 protonated arylons, 39 bridged arylons, 6 carboxylons, 5 alkyl-substituted carbons, 2 oxygen-substituted carbons, 4 methylene carbons, and 3 methylons. The established 2D molecular structure formula was C152H82O12N2. The final 3D macromolecular structure model consisted of 14 2D molecular structures (structural formula C2128H1148O168N28), with the density set to 1.77 cm3/g, compressed in a cubic cell with an edge length of 3.05 nm. Finally, the adsorption results showed that the experimental adsorption of CO2 adsorption was less than the simulated adsorption, completing the validation of the model. The above study provides a method for determining the molecular structure of kerogen in the Longmaxi Formation shale, which can guide the study of the pore structure characteristics of the Longmaxi Formation shale.

Spatial distribution characteristics of soil organic matter in different land uses and its coupling with soil animals in the plateau basin in the South China Karst basin

Spatial distribution characteristics of soil organic matter in different land uses and its coupling with soil animals in the plateau basin in the South China Karst basin

Soil Microbial Community in 47 Chinese Forest Sites: Biogeographic Patterns and Links With Soil Dissolved Organic Matter

AbstractSoils in forested ecosystems are extremely heterogeneous and represent a critical component of terrestrial ecosystems. Despite their substantial ecological value, the geographic characteristics, ecological processes, and coexistence of microbial communities in forest soils remain poorly understood. Here, we investigated the biodiversity dynamics, environmental influences, community assembly, and co‐occurrence patterns of bacterial and fungal communities in surface and subsurface soils across 47 Chinese forest sites. The biogeographic characteristics determined using high‐throughput sequencing data sets revealed evident spatial patterns of bacterial and fungal α and β diversity, assembly processes, and co‐occurrence relationship, with greater variation in the bacterial than in fungal communities. Both fungal and bacterial communities showed significant spatial separations regulated by community assembly processes, co‐occurrence patterns, and soil variables. The microbial dissimilarity was lower in high latitudes than in low latitudes, which was consistent with the lower deterministic processes and relatively higher co‐occurrence associations in high latitudes than in low latitudes. Additionally, there were significant associations of soil dissolved organic matter (DOM) characteristics (e.g., its content, aromaticity, and molecular weight) with biodiversity dissimilarities, microbial assembly process balances, and microbial co‐occurrence relationships in bacterial and fungal communities; they clearly indicate the key role of DOM in regulating microbial biogeographic patterns in forest soil ecosystems. Collectively, our study enhances the understanding of biogeographic patterns and coexistence theories in forest soil microbial ecosystems.

Quantifying particulate organic matter: source composition and fluxes at the river-estuary interface

Particulate organic matter (POM) characteristics and variability have been widely studied along the land-ocean aquatic continuum, yet, gaps remain in quantifying its source composition, fluxes, and dynamics at the river-estuary interface. POM in rivers consists of a complex mixture of sources, derived both from locally produced (i.e. phytoplankton) and from adjacent ecosystems (e.g. terrestrial POM). Each source differ in its trophic and biogeochemical characteristics, hence impacting its integration into local food webs, its transfer to estuaries and sea, and its contribution to biogeochemical processes. In this study, we use a robust approach based on in situ POM to characterize river POM end-members, to quantify POM composition and dynamics, and to identify the related key drivers. This study was performed at the River-Estuary interface of one of the main rivers in Western Europe (the Loire River, France). For 3 years, we conducted bimonthly measurements of carbon and nitrogen isotopic (δ13C, δ15N) and elemental (C/N) ratios to quantify the contribution of two sources (phytoplankton and terrestrial POM) to the POM mixture and calculated annual fluxes of particulate organic carbon (POC) and nitrogen (PN) sources. Throughout the year, POM consisted of ~65% phytoplankton and 35% terrestrial POM. The mean annual export fluxes were 40.6 tPOC/year and 2.45 tPN/year over the studied period, with half of it originating from phytoplankton (53 and 55% for POC and PN, respectively). We observed a clear seasonal pattern in POM composition: phytoplankton predominated from March to October, in relation to high primary production, while terrestrial contributions were the highest from November to February, driven by greater autumn-winter hydrodynamics. Our study illustrate the interest of such an approach to quantify POM composition in aquatic system and estimate source fluxes, and provide fundamental results for estimating seasonal baselines in food webs, establishing biogeochemical budgets, and quantifying POM exports to estuarine and marine environments. Applying this methodology across a broad spectrum of aquatic systems should enhance our understanding of biogeochemical processes and organic matter transformation along the land-ocean continuum and illustrates the contribution of these ecosystems to global biogeochemical cycles.

Fe(III)-mediated changes in microalgae-associated bacterial communities and dissolved organic matter characteristics: A case study for Chlorococcum sp. GD

Trivalent iron ions (Fe(III)) have important effects on aquatic ecosystems, especially on the functional diversity and stability of microorganisms and ecosystems. Here, a cultivable microalgae (Chlorococcum sp. GD) from the natural environment (Shanxi, China) were isolated and identified. A combined high-throughput 16S rRNA gene amplicon sequencing/excitation-emission matrix coupled with parallel factor (EEM-PARAFAC) analysis was used to integrated the results of Fe(III) influence on Chlorococcum sp. GD bacterial community and dissolved organic matter (DOM) characteristics through laboratory experiments. Due to the addition of Fe(III) in the form of ferric nitrate (Fe(NO3)3·9H2O), complexed with EDTA to maintain solubility and bioavailability, the bacterial community was altered. This led to a decrease in the relative abundance of Proteobacteria and Actinobacteria and an increase in the relative abundance of Cyanobacteria, especially under excessive Fe(III) treatment. In addition, the relative contribution of bacterial community dispersal limitation and homogenizing dispersal was 100 %, which may lead to differences in their local adaptation and ecological processes with homogenization of bacterial diversity and loss of function. Excessive Fe(III) caused a significant increase in the abundance of genes involved in the carbon cycle (p < 0.01) and a significant decrease in genes involved in the nitrogen cycle (p < 0.01), further affecting the overall regulatory network of gene expression. This led to an increase in the abundance of genes involved in metabolism, cellular processes, environmental information processing, genetic information processing, and human diseases. The moderate amount of Fe(III) promoted the production of microbial components and accelerated the degree of DOM humification. It is also worth mentioning that excessive Fe(III) inhibited DOM degradation. Overall, this work explored the characteristics of bacterial community and DOM changes in Fe(III)-stressed Chlorococcum sp. GD as an example, which contributes to an in-depth understanding of microbial community diversity and element cycling in aquatic ecosystems.

Improved Characterization of Soil Organic Matter by Integrating FT-ICR MS, Liquid Chromatography Tandem Mass Spectrometry, and Molecular Networking: A Case Study of Root Litter Decay under Drought Conditions.

Understanding of how soil organic matter (SOM) chemistry is altered in a changing climate has advanced considerably; however, most SOM components remain unidentified, impeding the ability to characterize a major fraction of organic matter and predict what types of molecules, and from which sources, will persist in soil. We present a novel approach to better characterize SOM extracts by integrating information from three types of analyses, and we deploy this method to characterize decaying root-detritus soil microcosms subjected to either drought or normal conditions. To observe broad differences in composition, we employed direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). We complemented this with liquid chromatography tandem mass spectrometry (LC-MS/MS) to identify components by library matching. Since libraries contain only a small fraction of SOM components, we also used fragment spectral cosine similarity scores to relate unknowns and library matches through molecular networks. This integrated approach allowed us to corroborate DI-FT-ICR MS molecular formulas using library matches, which included fungal metabolites and related polyphenolic compounds. We also inferred structures of unknowns from molecular networks and improved LC-MS/MS annotation rates from ∼5 to 35% by considering DI-FT-ICR MS molecular formula assignments. Under drought conditions, we found greater relative amounts of lignin-like vs condensed aromatic polyphenol formulas and lower average nominal oxidation state of carbon, suggesting reduced decomposition of SOM and/or microbes under stress. Our integrated approach provides a framework for enhanced annotation of SOM components that is more comprehensive than performing individual data analyses in parallel.

Unravelling the thermodynamic properties of soil ecosystems in mature beech forests

Thermodynamics is a vast area of knowledge with a debatable role in explaining the evolution of ecosystems. In the case of soil ecosystems, this role is still unclear due to difficulties in determining the thermodynamic functions that are involved in the survival and evolution of soils as living systems. The existing knowledge is largely based on theoretical approaches and has never been applied to soils using thermodynamic functions that have been experimentally determined. In this study, we present a method for the complete experimental thermodynamic characterization of soil organic matter. This method quantifies all the thermodynamic functions for combustion and formation reactions which are involved in the thermodynamic principles governing the evolution of the universe. We applied them to track the progress of soil organic matter with soil depth in mature beech forests. Our results show that soil organic matter evolves to a higher degree of reduction as it is mineralized, yielding products with lower carbon but higher energy content than the original organic matter used as reference. These products have higher entropy than the original one, demonstrating how the soil ecosystem evolves with depth, in accordance with the second law of thermodynamics. The results were sensitive to soil organic matter transformation in forests under different management, indicating potential applicability in elucidating the energy strategies for evolution and survival of soil systems as well as in settling their evolutionary states.

Unraveling the impact of Spartina alterniflora invasion on greenhouse gas production and emissions in coastal saltmarshes: New insights from dissolved organic matter characteristics and surface-porewater interactions

Saltmarshes along the Chinese coast are threatened by the invasion of Spartina alterniflora (S. alterniflora). This study was carried out in the Andong Shoal, Hangzhou Bay, China, with the aim of comprehending the intricate impacts of S. alterniflora invasion on greenhouse gases (GHG) production and emissions. To address this issue, we thoroughly examined the chemistry of dissolved organic matter (DOM) and the rate of surface water-porewater interaction. Porewater and surface water samples were collected from farm land, S. alterniflora invaded areas, and Scirpus mariqueter (S. mariqueter) dominated areas. The findings indicated that the invasion of S. alterniflora impeded the interaction between surface water and porewater, resulting in reduced porewater exchange rates within its affected region (0.015–0.440 cm d−1), in contrast to areas dominated by S. mariqueter (9.635–18.232 cm d−1). The invasion also increased dissolved organic carbon concentration in porewater and created a stable and closed soil environment that resulted in DOM with smaller molecule sizes and higher humification levels. The presence of high tryptophan-like fluorescent DOM caused an increase in the production of methane and carbon dioxide in S. alterniflora invaded area. However, both limited surface-porewater exchange and significant differences in GHG concentrations between porewater and surface water suggested that the aerenchyma tissues of S. alterniflora may play an important role in transporting GHG from soil to the atmosphere.