Refractory Carbon Research Articles

Additionality in Blue Carbon Ecosystems: Recommendations for a Universally Applicable Accounting Methodology.

Blue carbon ecosystems (BCEs) remove carbon dioxide from the atmosphere and store significant amounts of organic carbon (OC) in their soils. Consequently, the protection and restoration of BCEs may contribute to net greenhouse gas emissions abatement and help address the global challenges of both mitigating and adapting to climate change. An ongoing debate is whether OC sequestered out with the blue carbon (BC) project and transported to its present location (allochthonous) should be counted as 'additional'. There are inconsistencies in the treatment of allochthonous carbon between BCE methodologies, potentially undermining the credibility of global BC accounting initiatives. To explore these inconsistences, we compare the methodologies which we were able to find online, with particular focus on the VERRA, IPCC and BlueCAM methodologies, and review the science underlying any approach to account for allochthonous OC. Our findings indicate that there are currently no robust scientific approaches to define an appropriate apportioning of allochthonous OC for discounting in the calculation of additionality. We therefore advocate for the inclusion of allochthonous OC in BC crediting projects when an observational and experimental approach does not support the calculation (and discounting) of the refractory allochthonous carbon contribution.

Improved solid-state 13C and 15N NMR reveals fundamental compositional divide between refractory dissolved organic carbon and nitrogen in the sea

Marine dissolved organic matter (DOM) is one of the largest reservoirs of organic carbon and nitrogen in the world. Yet, despite its global importance, most DOM remains molecularly uncharacterized. Solid-state nuclear magnetic resonance (NMR) spectroscopy of isolated DOM fractions represents one of the most powerful techniques to understand overall structural composition. However, it is well known that standard cross polarization magic angle spinning (CP/MAS) NMR, the technique used for almost all past solid-state NMR studies of DOM, is at best “semi-quantitative,” and underestimates fully substituted NMR active nuclei. Additionally, almost all past solid-state NMR work analyzed high molecular weight (HMW) material isolated by ultrafiltration, which is now understood to represent mostly 14C-young, “semi-labile” compounds. In contrast, there is far less information regarding the composition of older, low molecular weight (LMW) DOM, which represents the vast majority of the ocean’s accumulated refractory DOM pool.Here, we applied 13C and 15N solid-state multiCP/MAS NMR, improved NMR methods optimized to more quantitatively resolve fully substituted NMR nuclei, to both HMW and LMW DOM isolated from the surface and deep North Pacific Subtropical Gyre. These methods confirm past work indicating most nitrogen containing HMW DOM as amide compounds, but also demonstrate a modest heterocyclic N component not previously identified. In contrast, we found that LMW DON is almost entirely aromatic heterocyclic N, consistent with the hypothesis that heterocyclic N structures may be largely responsible for the accumulation of the ocean’s refractory DON pool. Surprisingly, however, we find DOC aromatic functionalities still represent only a very minor portion of either the HMW or the LMW refractory carbon pools, in marked contrast to refractory DON composition. Together, these more quantitative solid-state NMR techniques likely represent the most accurate picture of DON and DOC functional and compound-class makeup to date, and so have broad implications for our understanding of marine DOM structure and cycling. Specifically, our new data suggests that while chemical composition likely acts as a key control on DOM lability, the most refractory components of DOC and DON have very different compositions, sources, and cycling, supporting the idea that DOC and DON cycling in the ocean may be largely decoupled.

Positive Effect of Biochar Application on Soil Properties: Solubility and Speciation of Heavy Metals in Non-Acidic Contaminated Soils near a Steel Metallurgical Plant in Southeastern Europe

Neutral and slightly alkaline arable soils from the vicinity of the former and the biggest metallurgical plant in southeastern Europe were analyzed for the status of the water soluble pool of heavy metals in 1–20% w/w biochar (BC)-amended contaminated soils. Heavy metal solubility was monitored over a 6-month period. The metals (Fe, Mn, Cu, Zn, Cd, Pb and Ba) exhibited significant relationships between each other and exceeded the maximum permissible concentrations (MPC) in surface waters for domestic and drinking purposes. In most of the investigated sites and BC treatments, metal concentrations decreased with time due to the transfer to more resistant soil pools. Cation exchange capacity, exchangeable Ca and pH increased after BC application, while electrical conductivity decreased. BC amendment led to the prevalence of humic acids (HAs) over fulvic acids (FAs) and increased the fraction of refractory organic carbon. The share of metal–organic complexes increased for the metals Zn, Cd, Mn and Ba in the BC-amended soils, and the share of free Me2+ species decreased. This trend was especially pronounced in the soils with the lowest pH of 6.4–6.9. In addition to improving soil physicochemical and ecochemical properties, biochar application contributed to metal species in solutions that were less mobile and bioavailable.

Additive manufacturing of copper parts using extrusion and sinter-based technology: evaluation of the influence of printing parameters and debinding method

PurposeThis work is focused on the realization of copper parts using the material extrusion additive manufacturing debinding and sintering (MEX+D&S) technology.Design/methodology/approachA highly filled filament with 90 Wt.% of copper is used to realize nine different combinations varying the printing speed and the flow rate. The following thermal debinding and sintering are performed at 483 °C and 1057 °C, respectively, burying the samples in specific refractory powder and carbon. The green and sintered density are measured and an inspection at optical microscope is implemented for a detailed internal analysis of the defects.FindingsThe samples, that reported the highest values of the green density, become the worst in the sintered condition due to evident swelling defect generated by the entrapped polymer during the thermal debinding. On the other hand, the parts with the lower values of green density allowed to achieve a satisfying density value without significant external defects.Originality/valueThe realization of copper parts through laser-based additive manufacturing technologies shows several troubles related to the rapid heat transfer and the high reflectivity of copper, which is a hinder of the absorption of the laser power. The MEX+D&S becomes an easier and economical alternative for the realization of copper parts. The internal inspection of the samples revealed the need for the improvement on the process chain, adopting a different debinding process to open channels during the thermal debinding to avoid the entrapment of the polymer.

Microbial stratification and DOM removal in drinking water biofilters: Implications for enhanced performance

Biofiltration is a low-cost, low-energy technology that employs a biologically activated bed of porous medium to reduce the biodegradable fraction of the dissolved organic matter (DOM) pool in source water, resulting in the production of drinking water. Microbial communities at different bed depths within the biofilter play crucial roles in the degradation and removal of dissolved organic carbon (DOC), ultimately impacting its performance. However, the relationships between the composition of microbial communities inhabiting different biofilter depths and their utilisation of various DOC fractions remain poorly understood. To address this knowledge gap, we conducted an experimental study where microbial communities from the upper (i.e., top 10 cm) and lower (i.e., bottom 10 cm) sections of a 30-cm long laboratory-scale biofilter were recovered. These communities were then individually incubated for 10 days using the same source water as the biofilter influent. Our study revealed that the bottom microbial community exhibited lower diversity yet had a co-occurrence network with a higher degree of interconnections among its members compared to the top microbial community. Moreover, we established a direct correlation between the composition and network structure of the microbial communities and their ability to utilise various DOM compounds within a DOM pool. Interestingly, although the bottom microbial community had only 20 % of the total cell abundance compared to the top community at the beginning of the incubation, it utilised and hence removed approximately 60 % more total DOC from the DOM pool than the top community. While both communities rapidly utilised labile carbon fractions, such as low-molecular-weight neutrals, the utilisation of more refractory carbon fractions, like high-molecular-weight humic substances with an average molecular weight of more than ca. 1451 g/mol, was exclusive to the bottom microbial community. By employing techniques that capture microbial diversity (i.e., flow cytometry and 16S rRNA amplicon sequencing) and considering the complexities of DOM (i.e., LCOCD), our study provides novel insights into how microbial community structure could influence the microbial-mediated processes of engineering significance in drinking water production. Finally, our findings could offer the opportunity to improve biofilter performances via engineering interventions that shape the compositions of biofilter microbial communities and enhance their utilisation and removal of DOM, most notably the more classically humified and refractory DOM compound groups.

Fire suppression interacts with soil acidity to maintain stable recalcitrant pyrogenic carbon fractions in South African mesic grasslands soil

Grassland ecosystems have evolved alongside fire, a fundamental element that shapes and sustains their ecological balance. Recent research indicates that carbon produced during pyrogenic events in fire-dependent ecosystems may occur in more recalcitrant forms within deeper soil horizons. Notably, refractory organic carbon (ROC) and black carbon (BC) fractions are globally recognised as highly stable components of soil carbon. Here, we examined the impact of prescribed fires on the accumulation of ROC and BC fractions within South African mesic grassland soils. Our findings revealed that while BC remains stable in the soil, exhibiting consistent levels across soil horizons, increased fire frequency led to breakdown of BC in the soil. Greater BC quantities were observed in burn exclusion and prescribed burns with a greater burn interval, suggested as primarily driven by a decline in soil pH. There were no significant differences in ROC within the burn treatments, but there was a notable decrease in ROC with increasing depth increments below 5 cm. The observed trend of ROC accumulation in the top layer of soil, influenced by

The Hunt for Chemical Dark Matter across a River-to-Ocean Continuum.

Thousands of mass peaks emerge during molecular characterization of natural dissolved organic matter (DOM) using ultrahigh-resolution mass spectrometry. While mass peaks assigned to certain molecular formulas have been extensively studied, the uncharacterized mass peaks that represent a significant fraction of organic matter and convey biogenic elements and energy have been previously ignored. In this study, we introduce the term dark DOM (DDOM) for unassigned mass peaks and have explored its characteristics and environmental behaviors using a data set of 38 DOM extracts covering the Yangtze River-to-ocean continuum. We identified a total of 9141 DDOM molecules, which exhibited higher molecular weight and greater diversity than the DOM subset with assigned DOM formulas. Although DDOM contributed a smaller fraction of relative abundance, it significantly impacted the molecular weight and molecular composition of bulk DOM. A portion of DDOM with higher molecular weight was found to increase molecular abundance across the river-to-ocean continuum. These compounds could contain halogenated organic molecules and might have a high potential to contribute to the refractory organic carbon pool. With this study, we underline the contribution of dark matter to the total DOM pool and emphasize that more DDOM research is needed to understand its contribution to global biogeochemical cycles and carbon sequestration.

Polystyrene microplastics facilitate formation of refractory dissolved organic matter and reduce CO2 emissions

Microplastics, as a type of anthropogenic pollution in aquatic ecosystems, affect the carbon cycle of organic matter. Although some studies have investigated the effects of microplastics on dissolved organic matter (DOM), the impact of alterations in the chemical properties of microplastics on refractory DOM and carbon release remains unclear. Here, we observed that microplastic treatments (e.g., polystyrene, PS) altered the composition and function of microbial community, notably increasing the abundance of microbial families involved in consuming easily degradable organic matter. During the process in which microbial community decomposed organic matter into DOM, PS underwent surface oxidation. The oxidized PS aggregated with DOM and microorganisms through electrostatic interactions and chemical bonds. Moreover, these interactions between oxidized PS and microbial community affect the utilization of organic matter, resulting in a significant decrease in CO2 emissions. Specifically, total CO2 emissions decreased by approximately 23.76 % with 0.1 mg/L PS treatment and by 44.97 % with 10 mg/L PS treatment compared to those in PS-free treatments over the entire reaction. These findings underscored the significance of the chemical properties of PS in the interactions among DOM and microorganisms, emphasizing the potential impact of PS microplastics on the carbon cycle in ecosystems.

Dual-carbon isotope analysis of benzene polycarboxylic acids for tracking black carbon across different environments

Black carbon (BC) is ubiquitous in the environment and is a significant component of the refractory carbon pool. However, its sources, biogeochemical processes, and environmental residence times are poorly understood. One important reason is that the technical protocols for isolating/analyzing BC vary across different matrices, thereby bringing inconsistency among studies on BC in different environment media. Benzene polycarboxylic acids (BPCA), produced by nitric acid oxidation of the condensed aromatic structure that is common in BC and BC-like substances, has been proven to be a useful molecular proxy for tracking BC in the Earth's surface. Here, we introduce a new technical approach for the compound-specific dual-carbon isotope (δ13C and Δ14C) analysis of BPCA. The BPCA compounds are isolated using preparative liquid chromatography, in which trifluoroacetic acid is used in the mobile phase instead of phosphoric acid. This allows complete removal of solvent from the isolated BPCA fraction, so that conversion of BPCA isolates into CO2 can be done by conventional oxidation methods for off-line Δ14C analysis with accelerator mass spectrometry. Liquid chromatography (void column)-stable carbon isotope ratio mass spectrometry is employed to measure δ13C of the isolated BPCA, leaving as much BPCA carbon amount as possible for 14C analysis. Blockage of oxidation chamber due to incomplete oxidation of other organic acids in the samples is avoided thanks to preliminary isolation of BPCA. We tested the approach by applying it to solid and dissolved BC species in a suite of environmental reference materials, including maize char, coal, riverine natural organic matter (NOM 2R101N), marine sediment (SRM 1941b), urban dust (SRM 1649b), and coke-polluted soils. We assessed the offsets of BPCA-δ13C and BPCA-Δ14C values caused by procedural carbon contaminations to correct measured carbon isotopic values. Paired δ13C-Δ14C data of individual BPCA were plotted to validate and demonstrate the ability of this dual carbon isotope technique in tracking BC across different environmental matrices. We observed slightly different δ13C-Δ14C signatures among individual BPCA, indicating that the less condensed BC may have younger apparent radiocarbon ages.

Amino acid carbon isotope profiles provide insight into lability and origins of particulate organic matter

AbstractIdentifying the phytoplankton origin of particulate organic matter (POM) in the deep ocean is challenging due to the changing phytoplankton composition and varied extent of decomposition by heterotrophic bacteria and zooplankton. Here, we report vertical distributions of amino acid stable carbon isotope values (δ13C) measured in particles in the South China Sea. Carbon‐weighted amino acid δ13C values generally parallel bulk POM δ13C profiles with a positive offset from 2.4‰ in the surface water to 6.0‰ in deep. Accordingly, a lability model is introduced to describe the relative distribution and isotopic linkage of labile and refractory particulate organic carbon. Temporal changes of amino acid δ13C were observed during the microbial decomposition of two phytoplankton strains, the prokaryote cyanobacterium Synechococcus and the eukaryote diatom Thalassiosira weissflogii. Principal component analysis of individual amino acid δ13C values from the decomposing cells separate samples into two components, reflecting the influence of microbial decomposition and taxonomic differences, respectively. These two components were further applied to particles. A major contribution from decomposing phytoplankton to particles below the euphotic zone was observed, with more prokaryote organic matter in the basin and a larger contribution from eukaryotes at stations near the productive northern shelf. Our findings show the applicability of amino acid δ13C values in tracing the lability and phytoplankton origins of POM in samples with varied extents of decomposition in marine environments.

Late Quaternary marine transgressions off the Shandong Peninsula inferred from paleosalinity indicators: Implications for Holocene mud wedge formation

Mud depocenters play an important role in the sediment source–sink system of marginal seas; however, the factors controlling the formation of mud deposits are not well understood. This study focused on Core LHSD-1, which is located on the southern margin of the Shandong Peninsula mud wedge in the northwestern part of the South Yellow Sea. Elemental ratios, such as the C/S ratio (the mass ratio of total organic carbon and total sulfur) and Sr/Ba ratio, were used to track the changes in paleosalinity during the late Quaternary and to investigate the mechanisms that influenced the formation of the mud wedge off the Shandong Peninsula. Our results indicate that Core LHSD-1 likely recorded two transgression events, corresponding to MIS3 and MIS1. Following sea-level rise after the Last Glacial Maximum (LGM), transgressive deposition began in the study area at approximately 11.5 kyr BP. During the early Holocene, fluctuating water salinity was recorded by Sr/Ba ratios, which became stable at approximately 6.8 kyr BP when the sea level reached its highstand. At the same time, the modern current system was established, and a significant amount of terrestrial material, such as refractory organic carbon and iron, has been transported to the study area by enhanced coastal currents, which was documented by elevated C/S ratios (C/S > 2.8) in mud sediments. Our findings indicate that marine transgressions controlled the initial development of the mud depocenter and that the establishment of the modern ocean current system promoted the rapid deposition of mud sediments, which corresponded to the growth of global mud depocenters.

The Vertical Metabolic Activity and Community Structure of Prokaryotes along Different Water Depths in the Kermadec and Diamantina Trenches.

Prokaryotes play a key role in particulate organic matter's decomposition and remineralization processes in the vertical scale of seawater, and prokaryotes contribute to more than 70% of the estimated remineralization. However, little is known about the microbial community and metabolic activity of the vertical distribution in the trenches. The composition and distribution of prokaryotes in the water columns and benthic boundary layers of the Kermadec Trench and the Diamantina Trench were investigated using high-throughput sequencing and quantitative PCR, together with the Biolog EcoplateTM microplates culture to analyze the microbial metabolic activity. Microbial communities in both trenches were dominated by Nitrososphaera and Halobacteria in archaea, and by Alphaproteobacteria and Gammaproteobacteria in bacteria, and the microbial community structure was significantly different between the water column and the benthic boundary layer. At the surface water, amino acids and polymers were used preferentially; at the benthic boundary layers, amino acids and amines were used preferentially. Cooperative relationships among different microbial groups and their carbon utilization capabilities could help to make better use of various carbon sources along the water depths, reflected by the predominantly positive relationships based on the co-occurrence network analysis. In addition, the distinct microbial metabolic activity detected at 800 m, which was the lower boundary of the twilight zone, had the lowest salinity and might have had higher proportions of refractory carbon sources than the shallower water depths and benthic boundary layers. This study reflected the initial preference of the carbon source by the natural microbes in the vertical scale of different trenches and should be complemented with stable isotopic tracing experiments in future studies to enhance the understanding of the complex carbon utilization pathways along the vertical scale by prokaryotes among different trenches.

Pyrogenic Carbon Degradation by Galvanic Coupling with Sprayed Seawater Microdroplets.

Surface waves are known for their mechanical role in coastal processes that influence the weather and climate. However, their chemical impact, particularly on the transformation of pyrogenic carbon, is poorly understood. Pyrogenic carbon is generally assumed to show negligible postformational alteration of its stable carbon isotope composition. Here we present an electrochemical interaction of pyrogenic carbon with the sprayed seawater microdroplets resulting from wave breaking, driven by the galvanic coupling between the microdroplet water-carbon interfaces and the microdroplet water-vapor interfaces. This enables refractory pyrogenic carbon to rapidly degrade via the oxygenation and mineralization reaction, which makes it ∼2.6‰ enriched in 13C, far exceeding the generally assumed postformation alteration values (<0.5‰) of pyrogenic carbon. The unique chemical dynamics of seawater microdroplets provide new insights into the discrepancy in carbon isotope signatures between riverine and marine black carbon, emphasizing the potential of coastal oceans for carbon sequestration in the global carbon cycle.

Natural organic small molecules promote the aging of plastic wastes and refractory carbon decomposition in water

Microplastics and nanoplastics are ubiquitous in rivers and undergo environmental aging. However, the molecular mechanisms of plastic aging and the in-depth effects of aging on ecological functions remain unclear in waters. The synergies of microplastics and nanoplastics (polystyrene as an example) with natural organic small molecules (e.g., natural hyaluronic acid and vitamin C related to biological tissue decomposition) are the key to producing radicals (•OH and •C). The radicals promote the formation of bubbles on plastic surfaces and generate derivatives of plastics such as monomer and dimer styrene. Nanoplastics are easier to age than microplastics. Pristine plastics inhibit the microbial Shannon diversity index and evenness, but the opposite results are observed for aging plastics. Pristine plastics curb pectin decomposition (an indicator of plant-originated refractory carbon), but aging plastics promote pectin decomposition. Microplastics and nanoplastics undergoing aging processes enhance the carbon biogeochemical cycle. For example, the increased carbohydrate active enzyme diversity, especially the related glycoside hydrolase and functional species Pseudomonas and Clostridium, contributes to refractory carbon decomposition. Different from the well-studied toxicity and aging of plastic pollutants, this study connects plastic pollutants with biological tissue decomposition, biodiversity and climate change together in rivers.

Factors driving the bioavailability of particulate organic matter in the Ross Sea (Antarctica) during summer

The biochemical composition and bioavailability of particulate organic matter (POM) were studied in relation to abiotic (water column stratification, macronutrient concentrations) and biotic factors (phytoplankton biomass and functional groups) in the open Ross Sea and coastal area of Terra Nova Bay, Antarctica, during the austral summer 2017. The presence of different sub-systems was highlighted by spatial and temporal variations of all the considered variables, characterised by higher concentrations of particulate organic carbon and nitrogen in Terra Nova Bay, where diatoms dominated, while in the open Ross Sea was higher the contribution of haptophytes (Phaeocystis antarctica Karsten, 1905). The southernmost Ross Sea was characterised by significantly higher concentrations of carbohydrates in the entire water column. High lipid contribution and low photosynthetic activity indicated aged POM, suggesting that POM was composed mainly by the remnants of previous haptophytes production. The higher lability of the carbohydrates indicated that an increase of haptophytes in the area could alter the biogeochemical C cycle, reducing the storage of refractory carbon in the depths, and favouring the transfer and respiration of C in the trophic web, with a decrease of export rate in the Ross Sea.

Benzenepoly(carboxylic acid)s as Exclusive Intrinsic Markers to Assess Riverine Export of Dissolved Black Carbon.

Landscape fires annually generate large quantities of black carbon. The water-soluble fraction of black carbon (i.e., dissolved black carbon/DBC) is an important constituent of the dissolved organic carbon (DOC) pool, playing a crucial role in the global budget of refractory carbon and climate change. A key challenge in constraining the flux and fate of riverine DBC is to develop targeted and accurate quantification methods. Herein, we report that benzenepentacarboxylic acid (B5CA) intrinsically present in DBC can be used as an exclusive and holistic marker (representing both condensed aromatics and less-/nonaromatic fractions) for DBC quantification. B5CA was universally detected in water extractions of biochar and fire-affected soils with relatively large abundance but not produced by nonthermogenic processes. It has good mobility in the environment as it is not readily precipitated by cations or adsorbed by common geosorbents. B5CA also represents the recalcitrant components of DBC with excellent stability against photodegradation and biodegradation. Applying B5CA as the DBC marker in surface waters of the Changjiang River (i.e., the third largest river in the world), we calculate the DBC concentration in the downstream Changjiang River to be 4.8 ± 5.5% of the DOC flux. Our work provides a simple and reliable approach for the accurate quantification and source tracking of DBC in the soil and aquatic carbon pools.

Peculiarities of obtaining nanocomposites with organic additives and consolidated nanomaterials with given properties

The work presents the results of the creation of consolidated nanomaterials and composite ceramics using modern methods of consolidation of ceramic materials for the synthesis of powder precursors and specified phases that self-reinforce ceramic matrices. The method of mechanosynthesis and electroconsolidation is used. The results of the use of these trends for the creation of promising composite materials are given. The use of mechanochemical synthesis of β-SiC nanoparticles in nanoreactors, involving the organic-inorganic complex (–CH3)–(SiO2)n and the modification of refractory filler powders and carbon bonds using silicon alkoxide and related gels, has been demonstrated to enable the production of composite materials. These materials are composed of SiC, WC, and ZrO2, exhibiting a minimum bending strength of 650 MPa and crack resistance ranging from 6.5–7.9 MPa m0.5. Furthermore, this method can also produce periclase-carbon materials known for their exceptional resistance to oxidation and slag.

Centennial-scale source shift in potentially toxic metal(loid)s in Yangtze River

Estuarine sedimentation is an important historical record of potentially toxic metal (PTM) emissions from human activities that can be used to improve environmental management. However, the contribution of different human activities to PTM deposition has not been accurately estimated, and their coupled relationship with riverine organic matter is typically not considered. In this study, we reconstruct the century-scale PTM depositional history of sediment cores from the Yangtze Grand Delta. Eight potential metal sources (PMSs) were identified using positive matrix factorization, and the results of lagged correlation determined the PMSs associated with the riverine discharge of the Yangtze River. Riverine PTMs were predominantly composed of Cr (79.0%), Ni (77.3%), and Pb (64.1%) but were deprived in Cu (34.9%). Glomalin-related soil protein (GRSP), which is a typical terrestrial refractory carbon, has a strong affinity for Cu, and contributed to 2.82–22.6% Cu deposition. The change in the PMS is mainly related to power generation, whereas the GRSP-bound PTM is mainly related to road construction and transportation. We advocate for responsible management of human activities in river catchments, particularly on coal-based power generation and road transportation, to maintain ecological security and promote the overall achievement of the Sustainable Development Goals.

Pyrogenic carbon stocks and its spatial variability in soils from savanna-forest ecotone in amazon

Forest fragments from Amazon are important long-term carbon (C) reservoirs with an essential role in the global C balance. They are often impacted by understory fires, deforestation, selective logging and livestock. Forest fires convert soil organic matter into pyrogenic carbon (PyC), but little is known about its distribution and accumulation along the soil profile. Thus, the objective of this study is to estimate the refractory carbon stocks derived from PyC accumulated in the soil vertical profile of different seasonal forest fragments in the Amazon. Sixty-nine soil cores (1 m deep) were collected in 12 forest fragments of different sizes considering edge and interior gradients. The mean total organic C (TOC) and PyC contents for the edge and interior gradients were 0.84% and 0.009%, respectively. The PyC/TOC ratio ranged from 0.53% to 1.78%, with an average of 1.32% and increasing in depth, being low when compared with other studies, where the contribution of PyC to TOC ranges from 1 to 9%. PyC stocks on the edge (1.04 ± 0.04 Mg ha−1) differed significantly from the interior (1.46 ± 0.03 Mg ha−1). The analyzed forest fragments presented a weighted PyC stock of 1.37 ± 0.65 Mg ha−1. The vertical distribution of PyC declined in depth with 70% of PyC concentrated in the surface soil layers (0–30 cm). These results indicate that the PyC accumulated in the vertical profile of soils in forest fragments in Amazonia are important, and they need to be considered in Brazilian and global reports on carbon stocks and fluxes.

The implication from six years of field experiment: the aging process induced lower rice production even with a high amount of biochar application

The single high-dose application of biochar to increase rice yield has been well reported. However, limited information is available about the long-term effects of increasing rice yield and soil fertility. This study was designed to perform a 6-year field experiment to unveil the rice yield with time due to various biochar application strategies. Moreover, an alternative strategy of the Annual Low dose biochar application (AL, 8 × 35% = 2.8 t ha−1) was also conducted to make a comparison with the High Single dose (HS, 22.5 t ha−1), and annual Rice Straw (RS, 8 t ha−1) amendment to investigate the effects on annual rice yield attributes and soil nutrient concentrations. Results showed that the rice yield in AL with a lower biochar application exceeded that of HS significantly (p < 0.05) in the 6th experimental year. The rice yield increased by 14.3% in RS, 10.9% in AL, and 4.2% in HS. The unexpectedly higher rice yield in AL than HS resulted from enhanced soil total carbon (TC), pH, and available Ca. However, compared to AL, liable carbon fraction increased by 33.7% in HS, while refractory carbon fraction dropped by 22.3%. Likewise, biochar characterization showed that more oxygen functional groups existed in HS than in AL. Decreasing inert organic carbon pools due to the constant degradation of the aromatic part of biochar in HS led to a lower soil TC than AL, even with a higher amount of biochar application. Likewise, the annual depletion lowered the soil pH and available Ca declination in HS. Based on the obtained results, this study suggested AL as a promising strategy to enhance rice productivity, soil nutrient enrichment, and carbon sequestration in the paddy ecosystem.Graphic abstract