Black Carbon In Soils Research Articles

Determination and Traceability of Black Carbon in Soil Around a Coal-fired Power Plant

Determination and Traceability of Black Carbon in Soil Around a Coal-fired Power Plant

Dosage- and site-dependent retention of black carbon and polycyclic aromatic hydrocarbons in farmland soils via long-term biochar addition

Biochar, a soil conditioner containing significant amounts of polycyclic aromatic hydrocarbons (PAHs), has gained widespread popularity in agricultural practices due to its advantages in improving soil fertility and carbon sequestration. While biochar may increase soil black carbon (BC) and PAH contents, the quantitative accumulation of BC and PAHs in different soil environments under varying biochar addition dosages remains poorly understood. Here, we investigated the content and composition of black carbon (evaluated using benzene polycarboxylic acids, BPCAs) and PAHs in soils treated with different biochar addition dosages from two long-term experimental farmlands in Ningxia (5-year) and Shandong (7- and 11-year), China. Results showed that increasing cumulative biochar dosage caused elevated contents of black carbon and PAHs, accompanied by decreases in their retention efficiencies. Contrasting retention was observed between sites, with the Shandong site characterized by higher retention efficiencies of BPCAs and lower retention efficiencies of PAHs, possibly owing to its higher temperature, more sandy soil texture, less irrigation, and lower sunlight intensity. Despite both black carbon and PAHs originating from biochar and sharing similar condensed aromatic structures, there was no significant correlation between the contents of black carbon and PAHs, indicating distinct behaviors and fates of these compounds. These findings emphasize the importance of optimizing biochar addition dosages and considering site-specific environmental factors for effective soil black carbon sequestration through biochar application.Graphical

Soil carbon determination for long‐term monitoring revisited using thermo‐gravimetric analysis

AbstractSoils and the vadose zone are the major terrestrial repository of carbon (C) in the form of soil organic matter (SOM), more resistant black carbon (BC), and inorganic carbonate. Differentiating between these pools is important for assessing vulnerability to degradation and changes in the C cycle affecting soil health and climate regulation. Major monitoring programs from field to continent are now being undertaken to track changes in soil carbon (SC). Inexpensive, robust measures that can differentiate small changes in the C pools in a single measurement are highly desirable for long‐term monitoring. In this study, we assess the accuracy and precision of thermo‐gravimetric analysis (TGA) using organic matter standards, clay minerals, and soils from a national data set. We investigate the use of TGA to routinely differentiate between C pools, something no single measurement has yet achieved. Based on the kinetic nature of thermal oxidation of SC combined with the different thermodynamic stabilities of the molecules, we designed a new method to quantify the inorganic and organic SC and further separate the organic biogeochemically active SOM (as loss on ignition, LOI) from the resistant BC in soils. We analyze the TGA spectrums of a national soil monitoring data set (n = 456) and measure total carbon (TC) using thermal oxidation and also demonstrate a TC/LOI relationship of 0.55 for soils ranging from mineral soils to peat for the United Kingdom consistent with previous monitoring campaigns.

Soil Black Carbon Increases Under Urban Trees with Road Density and Time: Opportunity Hotspots for Carbon Storage in Urban Ecosystems.

Black carbon (BC) can comprise a significant fraction of the soil carbon pool in cities. However, vegetation cover and human activity influence the spatial distribution of urban soil BC. We quantified soil total carbon (TC), soil organic carbon (SOC), BC, and total nitrogen (TN) in a medium-sized city in Dallas-Fort Worth, Texas. Soils were sampled to 20 cm depth from underneath 16 paired Quercus stellata (post oak) trees and open lawns. Effects of vegetation cover, road density, and building age (a proxy for time since development) on soil C and N were analyzed. Soil OC concentrations were higher under post oak trees (5.5%) compared to open lawns (3.6%) at 0-10 cm, but not at 10-20 cm depth. In contrast, soil BC and TN did not differ by vegetation cover. There were significant interaction effects between vegetation cover and road density and vegetation cover and building age on soil BC. At 0-10 cm, soil BC concentrations, stock, and BC/SOC ratios increased more with road density under trees than lawns, indicating enhanced atmospheric BC deposition to tree canopies. Black carbon in tree soils also increased with building age as compared to lawn soils, likely due to higher BC retention under trees, enhanced BC losses under lawns, or both. Our findings show that urban tree soils are localized opportunity hotspots for BC storage in areas with elevated emissions and longer time since development. Conserving and planting urban trees above permeable surfaces and soils could contribute to long-term carbon storage in urban ecosystems.

Transport pathways of black carbon to a high mountain Himalayan lake during late Holocene: Inferences from nitrogen isotopes of black carbon

Historically, forest fires have played a significant role in the production and distribution of black carbon (BC), including its deposition in water bodies. BC can reach to water bodies through two main pathways: (i) wet and dry atmospheric deposition and (ii) transportation of soil BC via surface runoff. Identifying the transport pathways of BC after fire has proven to be a challenging endeavour. This study aimed to decipher the pathway of BC transportation to a lake (Wular Lake, Kashmir Valley, India) by utilizing nitrogen isotopic composition of BC (δ15NBC) from a sediment core spanning 3744 years. The δ15NBC record demonstrate that terrestrial N dynamics in the Kashmir Valley were predominantly influenced by shifts in climate condition during the late Holocene. The observed variations indicated lower δ15NBC, indicative of dominance of atmospheric transportation of BC to the lake, during relatively drier periods with higher forest fire activity. In contrast, higher δ15NBC, suggesting a dominance of soil BC transportation via runoff, aligned with relative wetter periods of low forest fire activity.

Black carbon, soil organic matter molecular signatures under different land uses in Shenyang, China and relationship with PAHs

The content, composition and molecular signatures of soil organic matter (SOM) have important influences on the cycle of soil organic carbon (SOC) and the partitioning of polycyclic aromatic hydrocarbons (PAHs) in soil. Seventy-nine soil samples from farmland, forest and urban areas were collected in Shenyang, China to investigate black carbon (BC) content, SOM molecular signatures varied with land use patterns, as well as the relationship with PAHs. The content of BC in urban soils was significantly higher than that of farmland and forest. BC was a key contributor of urban SOM which accounted for 0.35 ± 0.31 of SOC in urban soil. Based on BC/SOC ratio, the main sources of BC were identified as fossil fuel combustion for urban soils, while for farmland and forest soils, it is the mixed results of fossil fuel combustion and biomass burning. All categories of PAHs in urban soils showed the highest level compared to farmland and forest soils. Pearson's correlation analysis results showed there were significant positive correlations between BC and PAHs categories in urban soils, indicating the important role of BC in the accumulation of PAHs in soil. SOM from each of the two different land use patterns can be distinguished by molecular signatures. Urban SOM had abundant molecular markers derived from condensed organic carbon inputs, which was consistent with the BC/SOC value. Farmland SOM had abundant carbon from vegetation and microorganisms, and forest SOM was rich in organic carbon from fresh plant materials. The markers enriched in urban SOM showed significant correlations with most PAHs categories, highlighting the affinity of urban SOM for PAHs at the molecular level. This study contributed to understanding the impact of land management methods on SOM molecular composition signatures and its influence on PAHs occurrence in soil, providing a theoretical basis for regional soil pollution management.

Diffuse Reflectance Spectroscopy for Black Carbon Screening of Agricultural Soils under Industrial Anthropopressure.

Visible and near-infrared spectroscopy (VIS-NIRS) is a fast and simple method increasingly used in soil science. This study aimed to investigate VIS-NIRS applicability to predict soil black carbon (BC) content and the method's suitability for rapid BC-level screening. Forty-three soil samples were collected in an agricultural area remaining under strong industrial impact. Soil texture, pH, total nitrogen (Ntot) and total carbon (Ctot), soil organic carbon (SOC), soil organic matter (SOM), and BC were analyzed. Samples were divided into three classes according to BC content (low, medium, and high BC content) and scanned in the 350-2500 nm range. A support vector machine (SVM) was used to develop prediction models of soil properties. Partial least-square with SVM (PLS-SVM) was used to classify samples for screening purposes. Prediction models of soil properties were at best satisfactory (Ntot: R2 = 0.76, RMSECV = 0.59 g kg-1, RPIQ = 0.65), due to large kurtosis and data skewness. The RMSECV were large (16.86 g kg-1 for SOC), presumably due to the limited number of samples available and the wide data spread. Given our results, the VIS-NIRS method seems efficient for classifying soil samples from an industrialized area according to BC content level (training accuracy of 77% and validation accuracy of 81%).

Identification of thermal signature and quantification of charcoal in soil using differential scanning calorimetry and benzene polycarboxylic acid (BPCA) markers

Abstract. Black carbon (BC) plays an important role in terrestrial carbon storage and can sustainably improve soil fertility. However, the accurate quantification of BC remains critical to fully unravelling the functions and dynamics of BC in soil. In this study, we explored the potential of differential scanning calorimetry (DSC) to identify, characterize and quantify charcoal in the soil of pre-industrial charcoal kiln sites from various forest and cropland areas in Belgium and Germany. Pre-industrial charcoals and uncharred soil organic matter (SOM) demonstrated a distinct thermal signature that could be used to distinguish between them, with charcoal being more thermally stable than SOM. The DSC pattern of charcoals was characterized by one to three specific exothermic peaks, varying in size and position depending on soil conditions. Our data suggest that the thermal moieties within charcoal depend on the strength of chemical bonds of C atoms (increasing with the degree of aromatic condensation and decreasing with weathering) and on the activation energy required to initiate combustion. Despite the specific thermal features of charcoal, its decomposition spans a wide range of temperatures that overlaps with the thermal signature of uncharred SOM. This stresses the challenge of BC quantification in soil and hinders the use of cut-off temperatures to accurately quantify charcoal in soil. Therefore, charcoal-C content was estimated from the relative height of exothermic peaks, attributed either to the combustion of charcoal or SOM. For a selection of 45 soil samples, charcoal-C content estimated by DSC was compared to benzene polycarboxylic acid (BPCA) abundance, a widely used method to quantify BC in soil. The two methods correlated strongly (R2=0.97), with BPCA C representing about one-fifth of DSC-derived charcoal C. This reinforces the view that operationally defined BC content has an absolute quantitative value only if the recovery rate is controlled, which is very complicated for many case studies. Overall, our results demonstrate that dynamic thermal analysis is largely under-exploited despite providing quantitatively interpretable information across the continuum of SOM.

Effects of Urbanization Intensity on the Distribution of Black Carbon in Urban Surface Soil in South China

Rapid urbanization causes the accumulation of large amounts of pollutants, including heavy metals, organic pollutants, and black carbon (BC). BC is the carbonaceous residue generated from the incomplete combustion of fossil fuels and biomass. It plays an important role on the migration of heavy metals and organic pollutants, as well as soil carbon sequestration. BC accumulation due to human activities greatly affects the global carbon budget, helps to drive climate change, and damages human health. To date, few studies have examined how the intensity of urbanization affects the distribution of BC in soils in urban areas. Therefore, the objective of this study is to determine the effects of urbanization intensity on the spatial distribution and content of BC in urban surface soil. We collected samples from 55 sites in South China and used a multi-scale geographical regression model to evaluate the impact of the interference intensity of urbanization on the amount and distribution of BC. Our results showed that the BC content was significantly higher in urban areas (9.74 ± 1.18 g kg−1) than in rural areas (2.94 ± 0.89 g kg−1) and that several urban parks with a higher interference intensity were hotspots of BC accumulation, suggesting that urbanization promoted BC accumulation. Our model revealed that road density was significantly and positively correlated with BC accumulation. Because there are more cars driving in areas with high road density, vehicle emissions may be one of the causes of BC accumulation. Our results also indicated that the impact of urbanization intensity on the BC distribution was sensitive to sampling density.

Black Carbon and Its Effect on Carbon Sequestration in Soil

The properties of black carbon (BC) are described very differently in the literature, even when determined by the same methodological procedure. To clarify this discrepancy, BC was investigated in the clay Cambisols of southern Bohemia, Czech Republic, in groups of soils with lower and higher deposition of its atmospheric fallout. The BC determination was performed according to a modified method of Kuhlbusch and Crutzen (1995). The amount of the free light fraction, the occluded light fraction of soil organic matter and its ratio, the amount of heavy soil fraction DF, and its soil organic matter DFOM were determined. Other soil characteristics were identified. It was found that there are two very different types of BC in soils. Historical BC from biomass fires, and new, anthropogenic, from the furnace and transport fumes. Historical BC has a significant effect on the organic matter of the heavy soil fraction, on the ratio of the free and occluded soil organic matter fraction, and the number of water-resistant soil aggregates. Anthropogenic BC does not have this effect. Because this form of BC is not significantly stabilized by the colloidal mineral fraction, it is necessary to take general data on BC’s high stability and resistance to mineralization in the soil with circumspection.

Opening the black box: Soil microcosm experiments reveal soot black carbon short-term oxidation and influence on soil organic carbon mineralisation

Soils hold three quarters of the total organic carbon (OC) stock in terrestrial ecosystems and yet we fundamentally lack detailed mechanistic understanding of the turnover of major soil OC pools. Black carbon (BC), the product of the incomplete combustion of fossil fuels and biomass, is ubiquitous in soils globally. Although BC is a major soil carbon pool, its effects on the global carbon cycle have not yet been resolved. Soil BC represents a large stable carbon pool turning over on geological timescales, but research suggests it can alter soil biogeochemical cycling including that of soil OC. Here, we established two soil microcosm experiments: experiment one added 13C OC to soil with and without added BC (soot or biochar) to investigate whether it suppresses OC mineralisation; experiment two added 13C BC (soot) to soil to establish whether it is mineralised in soil over a short timescale. Gases were sampled over six-months and analysed using isotope ratio mass spectrometry. In experiment one we found that the efflux of 13C OC from soil decreased over time, but the addition of soot to soil significantly reduced the mineralisation of OC from 32% of the total supplied without soot to 14% of the total supplied with soot. In contrast, there was not a significant difference after the addition of biochar in the flux of 13C from the OC added to the soil. In experiment two, we found that the efflux 13C from soil with added 13C soot significantly differed from the control, but this efflux declined over time. There was a cumulative loss of 0.17% 13C from soot over the experiment. These experimental results represent a step-change in understanding the influence of BC continuum on carbon dynamics, which has major consequences for the way we monitor and manage soils for carbon sequestration in future.

Heavy metals and metalloids concentrations across UK urban horticultural soils and the factors influencing their bioavailability to food crops

Urban horticulture (UH) has been proposed as a solution to increase urban sustainability, but the potential risks to human health due to potentially elevated soil heavy metals and metalloids (HM) concentrations represent a major constraint for UH expansion. Here we provide the first UK-wide assessment of soil HM concentrations (total and bioavailable) in UH soils and the factors influencing their bioavailability to crops. Soils from 200 allotments across ten cities in the UK were collected and analysed for HM concentrations, black carbon (BC) and organic carbon (OC) concentrations, pH and texture. We found that although HM are widespread across UK UH soils, most concentrations fell below the respective UK soil screening values (C4SLs): 99 % Cr; 98 % As, Cd, Ni; 95 % Cu; 52 % Zn. However, 83 % of Pb concentrations exceeded C4SL, but only 3.5 % were above Pb national background concentration of 820 mg kg−1. The bioavailable HM concentrations represent a small fraction (0.01–1.8 %) of the total concentrations even for those soils that exceeded C4SLs. There was a significant positive relationship between both total and bioavailable HM and soil BC and OC concentrations. This suggest that while contributing to the accumulation of HM concentrations in UH soils, BC and OC may also provide a biding surface for the bioavailable HM concentrations contributing to their immobilisation. These findings have implications for both management of the risk to human health associated with UH growing in urban soils and with management of UH soil. There is a clear need to understand the mechanisms driving soil-to-crop HM transfer in UH to improve potentially restrictive C4SL (e.g. Pb) especially as public demand for UH land is growing. In addition, the UH community would benefit from education programs promoting soil management practices that reduce the risk of HM exposure - particularly in those plots where C4SLs were exceeded.

Anthropogenic impacts recorded by a 200-year peat profile from the Zoige Peatland, northeastern Qinghai–Tibetan Plateau

Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) of peatlands are ideal natural archives of anthropogenic activities, but few comprehensive surveys have been carried out on the BC and PAHs of peatlands on the Qinghai–Tibet Plateau (QTP). To establish the fate of anthropogenic pollutants in peatlands, this study analyzed the 210Pb and 137Cs activities, concentrations of several chemical parameters, and the correlations between the soil properties, meteorological parameters, BC, and PAHs in a 30-cm peat profile from the Zoige Plateau, northeastern China. Our results reveal BC and total PAH concentration ranges of 39.9–82.6 mg.g−1 and 27.5–726.9 ng.g−1, respectively. Based on these results and our knowledge of social development in China and around the world, we divided the peat profile into three groups: 1824–1949 (i.e., before the New China foundation), 1950–1980s, and post-1980 s. The ratios of low- and high-molecular weight PAHs, BaA/(BaA + Chr) and Flu/(Flu + Pyr) were typically less than 1.00 and exceeding 0.35 and 0.40, respectively. These results indicate that anthropogenic impacts have had a serious impact on the QTP, and the PAHs in this area originated from the combustion of coal, biomass, and oil-related products. Moreover, the primary sources have shifted from local emissions to remote sources over the past 200 years.

Characteristics and Sources of Black Carbon and Organic Carbon in Topsoil from Different Functional Zones of Beijing, China

Considering human activities are the most direct and important factors leading to the accumulation and loss of soil black carbon (BC), a detailed understanding of soil BC in different functional zones and reasonable soil management are the keys to determine whether soil is the carbon source or carbon sink. In this study, carbon concentrations and isotope compositions of black carbon (BC%, δ13CBC) and organic carbon (OC, δ13COC) were determined in topsoil from different functional zones (roadside grass verges, parks, residential areas, mines, arable lands, woodlands and wastelands) in urban and suburban of Beijing, China. The organic carbon (OC) content in soils of the urban area (averaging 1.67%) is higher than in suburban areas (averaging 1.05%). Black carbon is not evenly distributed across different functional zones, but is more concentrated and variable in urban areas (0.11–2.43%, averaging 0.73%) than in suburban areas (0.03–0.70%, averaging 0.18%). The ratios of BC% to OC% in suburban areas (0.04–0.40) are smaller than in urban areas (0.15–0.98). The δ13CBC of topsoil (–26.35…–20.85‰) reflects that coal combustion has a strong impact on soil BC accumulation in Beijing. The carbon isotope differences between OC and BC of the suburban and urban topsoils are positive (averaging +0.56‰) and negative (averaging –0.41‰), respectively. This suggests that urban areas are seriously influenced by human activities which lead to a large amount of fossil fuel combustion, but suburban areas have received a uniform deposition of atmospherically transported finer BC aerosols.

Black Carbon in Surface Soil and Its Sources in Three Central Asian Countries.

Black carbon (BC) aerosol impacts the air quality, public health, agricultural productivity, weather, monsoon, cryosphere, and climate system from the local to the global scale. However, its distribution over vast Central Asia is poorly known, because it is one of the poorly sampled regions of the world. BC in the soil can be resuspended into the atmosphere and transported to downwind regions with sensitive ecosystems and vulnerable populations, such as from Central Asian countries to the cryospheric regions in the Tianshan Mountain and the Tibetan Plateau, which could accelerate the melting of the snowfields and glaciers. We report the distribution of BC and total organic carbon (TOC) in surface soil with samples collected at multiple sites, for the first time, over three countries in Central Asia (Uzbekistan, Tajikistan, and Kyrgyzstan). The mean BC (TOC) concentrations over three countries were 0.06 ± 0.06 (11.86 ± 4.84) mg g-1, 0.15 ± 0.21 (20.35 ± 10.96) mg g-1, and 0.32 ± 0.29 (26.45 ± 20.38) mg g-1, respectively. They were found to be originated from the same or similar sources, at least over Tajikistan and Kyrgyzstan, as indicated by their high and significant correlation (R2 > 0.6, p < 0.001). The char/soot ratio indicated the diesel and gasoline combustion as dominant BC sources over this region. To gain further insights into the soil BC and its implications to air quality, climate, and cryosphere, future studies should include a wider area over Central Asia with different land-use types and other soil parameters combined with atmospheric simulations for this important yet relatively less studied region of the world.

Relationships between dissolved black carbon and dissolved organic matter in streams

Black carbon (BC) is a pyrolyzed product derived from incomplete combustion. A major fraction of BC produced by landscape fires is initially deposited onto onsite soils. Atmospheric deposition of soot is known to be an important source of soil BC, especially in watersheds that are not affected by landscape fires. The transport of the dissolved fraction of oxidized BC in soil, defined as dissolved black carbon (DBC), to streams is considered one of the important loss pathways of BC in soil, but the mechanism is not well documented. We measured the quantity and quality of DBC, determined by a benzenepolycarboxylic acid method, and the quantitative and qualitative parameters of bulk dissolved organic matter (DOM) in streams in Hokkaido, northern Japan, whose catchments were not affected by landscape fire for at least 110 years. DBC with relatively low polycondensed signatures occurred in the streams, irrespective of differences in watershed characteristics and seasons, suggesting that atmospheric deposition of soot into the catchment is probably a major source of stream DBC. The DBC concentration was linearly related to the dissolved organic carbon (DOC) concentration, irrespective of the differences in watershed characteristics and seasons. Furthermore, the polycondensation degree of DBC was observed to correlate with the qualitative parameters of bulk DOM. Such quantitative and qualitative relationships between DBC and bulk DOM imply that the transfer mechanism from soils to streams of soot-derived polycondensed DBC is linked with that of higher plant-derived, high-molecular-weight aromatic DOM.

Effects of topographic factors on soil black carbon storage in coniferous forests at the north end of Greater Khingan Mountains

Effects of topographic factors on soil black carbon storage in coniferous forests at the north end of Greater Khingan Mountains

Background levels of OCPs, PCBs, and PAHs in soils from the eastern Pamirs, China, an alpine region influenced by westerly atmospheric transport

Long-range atmospheric transport (LRAT) plays a crucial role in the occurrence of persistent organic pollutants (POPs) in remote regions. When studying the LRAT of POPs on the Tibetan Plateau, westerly-controlled regions have received insufficient attention compared with regions influenced by the Indian monsoon or air flow from East Asia. We investigated the residual levels of POPs in soils from the eastern Pamirs and used air backward trajectory analysis to elucidate the influence of potential source regions via LRAT. Organochlorine pesticides (OCPs, mainly comprising DDTs, HCHs, and HCB), polychlorinated biphenyls (PCBs, mainly comprising penta- and hexa-CBs), and polycyclic aromatic hydrocarbons (PAHs, mainly comprising three- and four-ring) were detected at low concentrations of 40–1000, <MDL–88, and 2100–34,000 pg/g, respectively. We elucidated three major geographical distribution patterns of POPs, which were influenced by (1) the distribution of total organic carbon and black carbon in soil, (2) historical use of pesticides in the Tarim Basin, and (3) continuous emissions. Central Asia and the Tarim Basin were major potential source regions of POPs reaching the eastern Pamirs via LRAT. Historical use of technical HCH or lindane and technical DDT in potential source regions may contribute to the accumulation of HCHs and DDTs in the eastern Pamirs, respectively. Local sources seem to play a more important role in the occurrence of PAHs in the study area. By being under the control of less contaminated westerly air flow, the eastern Pamirs are more pristine than the core of the Tibetan Plateau where the Indian and East Asia monsoons deliver contaminants from highly industrialized areas in East China and India.

Leachable soil black carbon after biochar application

Black carbon (BC) enters soil via deposition of emissions and nowadays also via application of biochar. Recent studies indicate that a yet not quantified part of BC is lost from soil by leaching, which implies that BC exists in water-transportable form (so-called water-extractable BC; WEBC). We aim at quantifying the amount of WEBC in soil and at elucidating whether it relates to biochar application. The composition of WEBC was further tested to evaluate the degree of BC weathering over time after application, hypothesizing that BC degrades into smaller polyaromatic units. We analysed total BC and WEBC in topsoil (0–10 cm) of a field trial with application of 0, 4.5, and 9 Mg biochar ha−1 using the benzene polycarboxylic acid method. To see if there is a temporal relation between BC input and WEBC formation, we took samples directly after biochar application and three years later. Bulk BC and also WEBC concentrations increased with increasing biochar application rates. In contrast, WEBC portions of bulk BC decreased with increasing amount of applied biochar. On average, we found between 7.56 ± 2.50 and 12.56 ± 1.34 mg WEBC per kg agricultural soil, making up 0.6–1.84% of bulk BC. Over time, no loss or accumulation of either component was observed. However, we found that the composition of WEBC differed from bulk BC; i.e. WEBC consisted of less condensed aromatic structures than bulk BC indicating that de-condensation processes are involved in the formation of leachable BC.

Formation of Char-Like, Fused-Ring Aromatic Structures from a Nonpyrogenic Pathway during Decomposition of Wheat Straw.

Fused-ring aromatics, important skeletal components of black carbon (BC), contribute to long-term carbon (C) sequestration in nature. They have previously been thought to be primarily formed by incomplete combustion of organic materials, whereas the nonpyrogenic origins are negligible. Using advanced solid-state 13C nuclear magnetic resonance (NMR), including recoupled long-range C-H dipolar dephasing, exchange with protonated and nonprotonated spectral editing (EXPANSE), and dipolar-dephased double-quantum/single-quantum (DQ/SQ) spectroscopy, we for the first time identify fused-ring aromatics that formed during the decomposition of wheat (Triticum sp.) straw in soil under aerobic, but not anaerobic conditions. The observed formation of polyaromatic units as plant litter decomposes provides direct evidence for humification. Moreover, the estimation of the annual flux of such nonpyrogenic BC could be equivalent to 3-12% of pyrogenic BC added to soils from all other sources. Our findings significantly extend the understanding of potential sources of fused-ring aromatic C and BC in soils as well as the global C cycle.