Chemothermal Oxidation Research Articles

Characterizing sedimentary black carbon in the Pearl River Estuary, Southern China

Sedimentary black carbon in coastal regions plays an important role in global carbon cycles due to its refractory nature in sediments. In this study, we conducted the first comprehensive investigation on black carbon (BC) in surface sediments of the Pearl River Estuary (PRE), a large tropical estuary system in China. We used two different analytical methods: IMPROVE-A thermal optical reflectance (TOR) and chemothermal oxidation (CTO-375) to constrain the distribution, and TOR can further constrain the composition (i.e., char and soot). The BC concentration determined by the TOR method (BCTOR) ranged from 0.07 to 7.13 mg/g, with char and soot contents ranging from 0.04 to 6.98 mg/g and 0.03–0.43 mg/g, respectively. The BC concentrations measured by the CTO-375 method (BCCTO) ranged from 0.27 to 1.88 mg/g. Char was the predominant constituent (87%) of sedimentary BCTOR in the PRE. Both char and soot had higher concentrations locating near the outlets and on the Shenzhen coast, indicating that they were sourced through direct fluvial transport and surface runoff. Soot particles were transported farther from fluvial sources than char particles. We estimated that the burial flux of BCTOR in the PRE sediments was 2.97 ± 1.61 mg/cm2/yr, acting as an important sink of BC. This study implies that large river estuaries are hotspots for BC burial, sinking a large amount of organic carbon from terrestrial reservoirs.

Black Carbon in Deep-Sea Seamount Sediment Cores: Vertical Variation and Non-negligible Char Black Carbon.

Deep-sea sediments (>1000 m) are often considered to be the ultimate sink for black carbon (BC), and the long-term buried BC in these sediments is believed to potentially provide a negative feedback effect on climate warming. The burial flux of BC in marine sediments is predominantly estimated based on soot BC (SBC) in most studies, frequently ignoring the contribution of char BC (CBC). While this methodology may result in an underestimation of the BC burial flux, the precise extent of this underestimation is yet to be determined. This study used the benzene poly(carboxylic acid) (BPCA) method and chemothermal oxidation (CTO) method to analyze CBC and SBC in four deep-sea sediment cores from the Zhongnan seamount in the South China Sea, respectively. The CBC content increased from 0.026 ± 0.010% at the seamount upper part (1432 m) to 0.039 ± 0.012% at the seamount foot (4278 m), constituting approximately 25 to 42% of the SBC content. The content disparity between CBC and SBC diminishes as depth increases. In deep-sea sediments, biogeochemical factors influence the variation of CBC molecules with depth. In the seamount middle-upper part (1432 and 2465 m), highly condensed CBC gradually accumulated along the core downward profile. In the sediment core profile of the seamount middle-lower part (3497 m), benzenetricarboxylic acid and benzenetetracarboxylic acid content decreased while the BC condensation degree rose, i.e., less condensed CBC was preferentially consumed. Afterward, CBC molecules reached a relatively stable state at the seamount foot. This study reveals that CBC possesses the capacity for long-term carbon sequestration in deep-sea sediments, and its content is not negligible.

New insights on black carbon in pelagic Atlantic sediments

Black carbon (BC) is ubiquitous in pelagic sediments and presumed to have an older radiocarbon age due to long ocean residence times and pre-aging in terrestrial soils. Here, we analyzed sediments from five regions in the subtropical Atlantic Ocean to quantify the black carbon fraction of the total organic carbon pool. Black carbon, derived from the chemothermal oxidation method, comprised between 17 ± 6% of the sedimentary organic carbon in the Northwest Argentina Basin and 65 ± 18% in the Amazon Delta. Black carbon sediment accumulation rates were six times greater in the Sierra Leone Rise (8.4 ± 4.1 mg cm−2 kyr−1) compared to the remote Northwest Argentina Basin (1.3 ± 0.4 mg cm−2 kyr−1), possibly due to enhanced regional atmospheric deposition from annual African grassland fires. The radiocarbon age for BC from subtropical Atlantic sediments were more modern compared to the bulk total organic carbon, and BC source was apportioned as biomass burning byproducts from their stable carbon isotopic signatures and characteristic ratios of polycyclic aromatic hydrocarbons. This study demonstrated that subtropical Atlantic Ocean sediments serve as an important sink for young BC.

Mineral Soils Are an Important Intermediate Storage Pool of Black Carbon in Fennoscandian Boreal Forests.

Approximately 40% of earth's carbon (C) stored in land vegetation and soil is within the boreal region. This large C pool is subjected to substantial removals and transformations during periodic wildfire. Fire-altered C, commonly known as pyrogenic carbon (PyC), plays a significant role in forest ecosystem functioning and composes a considerable fraction of C transport to limnic and oceanic sediments. While PyC stores are beginning to be quantified globally, knowledge is lacking regarding the drivers of their production and transport across ecosystems. This study used the chemo-thermal oxidation at 375°C (CTO-375) method to isolate a particularly refractory subset of PyC compounds, here called black carbon (BC), finding an average increase of 11.6g BC m-2 at 1year postfire in 50 separate wildfires occurring in Sweden during 2018. These increases could not be linked to proposed drivers, however BC storage in 50 additional nearby unburnt soils related strongly to soil mass while its proportion of the larger C pool related negatively to soil C:N. Fire approximately doubled BC stocks in the mineral layer but had no significant effect on BC in the organic layer where it was likely produced. Suppressed decomposition rates and low heating during fire in mineral subsoil relative to upper layers suggests potential removals of the doubled mineral layer BC are more likely transported out of the soil system than degraded in situ. Therefore, mineral soils are suggested to be an important storage pool for BC that can buffer short-term (production in fire) and long-term (cross-ecosystem transport) BC cycling.

Sources, burial flux and mass inventory of black carbon in surface sediments of the Daya Bay, a typical mariculture bay of China

The contents of chemothermal oxidation (CTO)-derived black carbon (BC) and organic carbon (OC) and their stable isotopes (δ13CBC and δ13COC), including major elemental oxides, and grain sizes were measured to constrain the sources, burial flux, and mass inventory of BC in surface sediments of the Daya Bay. Surface sediments were mainly clayey silt (>90%) and contained 0.28–1.18% OC and 0.05–0.18% BC. Fossil fuel emission and physical erosion contributed to the sedimentary BC sources. High BC/OC ratio (6–30%), burial flux (154.88–922.67 μg cm−2 y−1), and mass inventory (22–34 Gg y−1) of BC in the upper 5 cm of surface sediments indicated that the Daya Bay is a significant sink of BC. The high accumulation of BC in sediments is attributed to a strong affinity to fine-grained sediments due to the enrichment of muddy biodeposits excrements from the cultured species in the bay.

Quantification methods of pyrogenic carbon in soil with soil as a complex matrix: comparing the CTO-375 and Cr2O7 methods

ABSTRACT Pyrogenic carbon (PyC) or black carbon (BC), the residue of grassland and forest fires and fossil fuel combustion, plays an important role in carbon storage and pollutant adsorption in soil. To understand its roles in soil, it is necessary to accurately assess the PyC fraction. Soil is, however, a complex mixture of inorganic and organic matter, usually containing humic substances, i.e., non-PyC organic matter, in concentrations one to two orders of magnitude higher than PyC. This engenders difficulty in determining the PyC content in soils; thus, various quantitative methods have been proposed for different research purposes. In this study, the two widely used methods of chemo-thermal oxidation at 375°C (CTO-375) and acid dichromate oxidation (Cr2O7) method were reconsidered in terms of the suitability for determining the PyC content of soil by using model soil. The CTO-375 method was simpler, but the quantified PyC was suggested to be the combustion residue of non-PyC organic matter. By contrast, 29 to 40% of PyC content was determined as non-PyC organic matter by the Cr2O7 method. Therefore, we proposed an improved Cr2O7 method by increasing acidic K2Cr2O7 concentration threefold for quantification accuracy: although time-consuming, it resulted in the lowest overestimation on the PyC content, that is, 16 to 23% from non-PyC organic matter. The application of the improved Cr2O7 method to natural soil was confirmed with 99 to 103% certainty (recovery rate).

Distribution and isotopic composition of sedimentary black carbon in a subtropical estuarine-coastal region of the western Taiwan Strait: Implications for tracing anthropogenic inputs

Estuarine and coastal margins are strongly influenced by anthropogenic inputs. To trace anthropogenic inputs to the subtropical Jiulong River Estuary (JRE) and the adjacent western Taiwan Strait (WTS), black carbon (BC) and its stable carbon isotope composition (δ13СBC) in surface sediments were investigated as an indicator of human activities. The concentrations of sedimentary BC were measured by an emerging method of thermal/optical reflectance with wet-chemical treatment (BCTOR, including char and soot), and the conventional method of chemothermal oxidation (BCCTO, related to the soot fraction) was also used to determine BCCTO concentrations and δ13СBC compositions. In the JRE and adjacent WTS, the concentrations of BCTOR (0.77 to 3.79 mg g−1) were higher than those of BCCTO (0.55 to 2.46 mg g−1), and both were similar to the moderate ranges obtained in other coastal sediments around the world. The small offsets between δ13СTOC and δ13СBC and the relatively low char/soot ratios revealed that fossil fuel combustion-derived contributions were likely more significant compared with inputs from biomass burning. The decreasing BC concentrations and increasing δ13СBC values with increasing distance from the JRE towards the adjacent WTS, indicates the decline of land-based anthropogenic inputs through fluvial transport. Furthermore, the differences in BC/TOC and char/soot values between the southern and northern WTS, indicated an effective preferential dispersal of the fluvial BC to the southern coast. The estimation for mass inventories of sedimentary BC in the coastal WTS showed that direct riverine discharge from the JRE was nearly equivalent to atmospheric deposition, and both of them contributed half of the sedimentary BC sink. To balance the sedimentary BC budget in the coastal WTS, long-range alongshore sediment transport driven by the Fujian-Zhejiang coastal current containing Yangtze River derived materials (indirect riverine discharge) could be another significant input pathway to contribute sedimentary BC.

Effects of Fire Severity and Topography on Soil Black Carbon Accumulation in Boreal Forest of Northeast China

Black carbon (BC) from incomplete combustion of biomass and fossil fuel is widespread in sediments and soils because of its high stability in nature and is considered an important component of the global carbon sink. However, knowledge of BC stocks and influencing factors in forest ecosystems is currently limited. We investigated soil BC contents in burned boreal forests of the Great Khingan Mountains, northeast China. We collected soil samples from 14 sites with different fire severities, slope positions and aspects. The samples were analyzed by the chemo-thermal oxidation method to obtain their BC concentrations. The BC concentrations of the studied soils ranged from 0.03 to 36.91 mg C g−1, with a mean of 1.44 ± 0.11 mg C g−1. BC concentrations gradually decline with depth, and that was significantly less in the 20–30 cm layer compared to all shallower layers. Forests burned by moderate-severity fires had the highest soil BC, the shady aspect had higher soil BC than the sunny aspect. Our results provide some basic data for evaluating the soil BC sink in boreal forests, which is a useful amendment to current carbon budget and carbon cycle in boreal forest ecosystems.

An improved method for quantitatively measuring the sequences of total organic carbon and black carbon in marine sediment cores

Understanding global carbon cycle is critical to uncover the mechanisms of global warming and remediate its adverse effects on human activities. Organic carbon in marine sediments is an indispensable part of the global carbon reservoir in global carbon cycling. Evaluating such a reservoir calls for quantitative studies of marine carbon burial, which closely depend on quantifying total organic carbon and black carbon in marine sediment cores and subsequently on obtaining their high-resolution temporal sequences. However, the conventional methods for detecting the contents of total organic carbon or black carbon cannot resolve the following specific difficulties, i.e., (1) a very limited amount of each subsample versus the diverse analytical items, (2) a low and fluctuating recovery rate of total organic carbon or black carbon versus the reproducibility of carbon data, and (3) a large number of subsamples versus the rapid batch measurements. In this work, (i) adopting the customized disposable ceramic crucibles with the microporecontrolled ability, (ii) developing self-made or customized facilities for the procedures of acidification and chemothermal oxidization, and (iii) optimizing procedures and carbon-sulfur analyzer, we have built a novel Wang-Xu-Yuan method (the WXY method) for measuring the contents of total organic carbon or black carbon in marine sediment cores, which includes the procedures of pretreatment, weighing, acidification, chemothermal oxidation and quantification; and can fully meet the requirements of establishing their highresolution temporal sequences, whatever in the recovery, experimental efficiency, accuracy and reliability of the measurements, and homogeneity of samples. In particular, the usage of disposable ceramic crucibles leads to evidently simplify the experimental scenario, which further results in the very high recovery rates for total organic carbon and black carbon. This new technique may provide a significant support for revealing the mechanism of carbon burial and evaluating the capacity of marine carbon accumulation and sequestration.

Century-scale high-resolution black carbon records in sediment cores from the South Yellow Sea, China

Black carbon (BC) has received increasing attention in the last 20 years because it is not only an absorbent of toxic pollutants but also a greenhouse substance, preserving fire-history records, and more importantly, acting as an indicator of biogeochemical cycles and global changes. By adopting an improved chemothermal oxidation method (WXY), this study reconstructed the century-scale high-resolution records of BC deposition from two fine-grained sediment cores collected from the Yellow Sea Cold Water Mass in the South Yellow Sea. The BC records were divided into five stages, which exhibited specific sequences with three BC peaks at approximately 1891, 1921, and 2007 AD, representing times at which the first heavy storms appeared just after the termination of long-term droughts. The significant correlation between the times of the BC peaks in the cores and heavy storms in the area of the Huanghe (Yellow) River demonstrated that BC peaks could result from markedly strengthened sedimentation due to surface runoff, which augmented the atmospheric deposition. Stable carbon isotope analysis indicated that the evident increase in carbon isotope ratios of BC in Stage 5 might have resulted from the input of weathered rock-derived graphitic carbon cardinally induced by the annual anthropogenic modulation of water-borne sediment in the Huanghe River since 2005 AD. Numerical calculations demonstrated that the input fraction of graphitic carbon was 22.97% for Stage 5, whereas no graphitic carbon entered during Stages 1 and 3. The obtained data provide new and important understanding of the source-sink history of BC in the Yellow Sea.

Pyrogenic carbon in Australian soils

Pyrogenic carbon (PyC), the combustion residues of fossil fuel and biomass, is a versatile soil fraction active in biogeochemical processes. In this study, the chemo-thermal oxidation method (CTO-375) was applied to investigate the content and distribution of PyC in 30 Australian agricultural, pastoral, bushland and parkland soil with various soil types. Soils were sampled incrementally to 50cm in 6 locations and at another 7 locations at 0–10cm. Results showed that PyC in Australian soils typically ranged from 0.27–5.62mg/g, with three Dermosol soils ranging within 2.58–5.62mg/g. Soil PyC contributed 2.0–11% (N=29) to the total organic carbon (TOC), with one Ferrosol as high as 26%. PyC was concentrated either in the top (0–10cm) or bottom (30–50cm) soil layers, with the highest PyC:TOC ratio in the bottom (30–50cm) soil horizon in all soils. Principal component analysis - multiple linear regression (PCA-MLR) suggested the silt-associated organic C factor accounted for 38.5% of the variation in PyC. Our findings suggest that PyC is an important fraction of the TOC (2.0–11%, N=18) and chemically recalcitrant organic C (ROC) obtained by chemical C fractionation method accounts for a significant proportion of soil TOC (47.3–84.9%, N=18). This is the first study comparing these two methods, and it indicates both CTO-375 and C speciation methods can determine a fraction of recalcitrant organic C. However, estimated chemically recalcitrant organic carbon pool (ROC) was approximately an order of magnitude greater than that of thermally stable organic carbon (PyC).

Assessment of distribution and sources of pyrogenic carbon in the lower course of the Guadiana River (SW Iberian Peninsula)

PurposeThe main goal of this work was to determine the pyrogenic carbon (PyC) distribution in surficial sediments for the last 40 km of the Guadiana River (SW Iberian Peninsula). In addition, the changes in the contribution of terrestrial and marine organic matter (OM) sources and their relationship with the PyC contents were assessed.Materials and methodsSediments were collected from 22 stations within the lower course of the Guadiana River. All the samples were analyzed for total organic carbon (TOC), total nitrogen (TN), organic carbon to nitrogen atomic ratios (C/N), and stable carbon isotope ratio (δ13C) as indicators of changes in the sources of OM. PyC was determined according to the chemo-thermal oxidation method (CTO-375).Results and discussionTOC ranged from 0.25 to 2.37 %dw. The greatest TOC contents were located in sediments collected at the middle estuary. The C/N values ranged from 7.7 to 12.7, with slight relative increase in the marine input compared to pre-Alqueva times. Similar C/N ranges are representative of native soil OM, lacustrine OM, and local sedimentary OM. The δ 13C values of the sediment samples ranged from –25.0 to –27.6 ‰ illustrating a signature of C3 higher plants, marsh-plants, lacustrine plants, and freshwater algae present in the area of study and in the forests located upstream. PyC ranged between 0.17 and 0.74 gkg−1, with the highest contents measured in samples located close to urbanized areas. Sediments collected at the middle estuary, within a rural area, showed the lowest proportions of PyC relative to the percent of TOC (≤4 % TOC). The negative relationship between PyC to TOC ratio and TOC contents confirmed the selective preservation of PyC to degradation in the sedimentary OM of the Guadiana estuary. The carbon isotope composition of the final material after applying the CTO-375 method (hereafter called δ13CPyC) was ˂–30 ‰, suggesting that the PyC fraction was mainly composed of a mixture of fossil fuels and C3-charred biomass. Nevertheless, selective loss of the less recalcitrant OM fractions due to degradation and/or chemical alteration might contribute to lighter carbon isotope values of PyC.ConclusionsGeochemical data showed that sedimentary OM was composed of a mix of different OM sources, with a slight increase in the marine input after the Alqueva dam went into operation. The PyC content was higher close to urbanized areas of the Guadiana River estuary. The selective preservation of PyC in the sedimentary OM of the Guadiana estuary was observed.

Black carbon in soils from different land use areas of Shanghai, China: Level, sources and relationship with polycyclic aromatic hydrocarbons

Black carbon (BC) in soils plays a key role of carrying hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs). However, little is known about the spatial distribution, sources of BC and its relationship with PAHs in urban soils. We studied BC, total organic carbon (TOC) and PAHs concurrently in 77 soils collected from downtown area, suburban and rural area and industrial area of Shanghai, China. BC was determined by both chemical oxidation (dichromate oxidation, BCCr) and chemo-thermal oxidation (CTO-375, BCCTO). BC sources were identified qualitatively by BC/TOC concentration ratios and BC-cogenerated high molecular weight (HMW) PAH isomer ratios and quantitatively by principal component analysis followed by multiple linear regression (PCA-MLR). Results showed that BCCr concentration (4.65g/kg on average) was significantly higher than BCCTO (1.91g/kg on average) in Shanghai soils. BCCr concentrations in industrial area were significantly higher than those in other two. Stronger correlation was found between PAHs and TOC, BCCr than that between PAHs and BCCTO, which indicates the possibility of PAHs being carried by charcoal and other organic matters thus negating its exclusive dependence on soot. Charcoal was therefore suggested to be taken into account in studies of BC and its sorption of PAHs. BC/TOC ratios showed a mixed source of biomass burning and fossil fuel combustion. PCA scores of BC-cogenerated HMW PAHs isomer ratios in potential sources and soil samples clearly demonstrated that sources of BC in urban soils may fall into two categories: coal and biomass combustion, and traffic (oil combustion and tire wear). PCA-MLR of HMW PAHs concentrations in soil samples indicated that coal and oil combustion had the largest contribution to BC in urban soils while tire wear and biomass combustion were important in downtown and rural area, respectively, which indicated they were main sources of HMW PAHs and presumably of BC.

Mineral-associated organic carbon and black carbon in restored wetlands

Stable soil organic carbon (SSOC) has a vital influence on soil's capacity for resisting disturbance and sequestering carbon. However, studies of the SSOC in restored wetlands are incomplete. We studied mineral-associated organic carbon (MOC) and black carbon (BC), two representatives of SSOC, in a wetland restoration chronosequence in Caizi Lake, East China. MOC was analyzed by both a physical method, involving dividing soil into size-fractions POM (>53 μm) and MOM (0.45–53 μm) and detecting OC in MOM (MOCP), and a chemical method, acidifying soil with hydrofluoric acid (HF) and detecting OC loss (MOCC). BC was analyzed by methods using dichromate (BCCr) and chemothermal oxidation (BCCTO). MOCC, BCCr, and BCCTO were further determined in MOM for comparing results from different fractions and methods. We found an elevation of soil ecological function in wetlands restored from farmlands in Caizi Lake, which was supported by a general increase of MOC and BC with time after restoration at surface soil (0–6 cm). Comparison of methods showed that size fractionation method overestimated MOC by identifying all OC in MOM as MOC, since HF-soluble OC accounted for no more than 23.5% of the whole OC in MOM. As it may separate more components, e.g. charcoal, from BC continuum, the dichromate method was recommended as more meaningful in the study of BC recovery in restored wetlands with biomass-burning history. We presented the possible use of ratio (BCCr–BCCTO):BCCTO for BC source identification which produced a reasonable result similar to that of a commonly used method. The combination of physical and chemical fractionation methods revealed that the proportion of BC to TOC in POM was considerable, which indicated that POM was not invariably labile as was commonly understood. Finally, a detailed list of soil organic carbon components including MOC, BC and labile OC in each size fraction was represented by using sequential analysis and combination of fractionation methods.

Validation and application of a thermal–optical reflectance (TOR) method for measuring black carbon in loess sediments

Three techniques were used to measure black carbon (BC) in samples from Chinese loess-paleosol sequences. The results obtained by (1) chemo-thermal oxidation (CTO, performed two ways), (2) acid dichromate oxidation (Cr2O7), and (3) thermal–optical reflectance (TOR) were intercompared because prior studies have shown that the methods can yield disparate results. BC concentrations did vary among the methods, most likely because they measured different components of the BC continuum, but the high-temperature BC (soot) determined by CTO was correlated with the BC and soot obtained by TOR. The CTO and TOR methods both yielded statistically significant linear relationships for loess and lake sediments that had incremental additions of a standard (SRM-1649a). The results also showed that charred material was more abundant in these test sediments than soot carbon. Data for BC in Luochuan loess generated using TOR showed a trend similar to that of magnetic susceptibility, that is, high BC and large susceptibilities during the last interglacial and low values for both variables in the last glacial. The results thus indicate that the TOR method is well suited for studies of sedimentary materials and that more biomass burned during the last interglacial than in the last glacial.

Stability and carbon isotope changes of soot and char materials during thermal oxidation: Implication for quantification and source appointment

The thermal-oxidative resistances of seven soot and char samples from various combustion processes were tested with a chemothermal oxidation (CTO) method. The residues of each soot/char oxidized at different temperature conditions were quantified for the remaining organic carbon contents and their stable carbon isotope compositions. The results showed that the soot/char samples had distinctly different resistance to CTO, with half-temperature values of 380–409°C for diesel- and hexane-derived soots, 276–312°C for biomass- and coal-derived soots, and 257–323°C for the other two chars. The lower thermal resistance of the two biomass soots and coal soot suggested that they likely were formed at lower combustion temperatures and that they cannot be detected or quantified in environmental samples using the standard CTO-375 method. The stable carbon isotope data showed three different modes of δ13C shifts as the combustion temperature increased. Both diesel and hexane soots had no change of δ13C values during CTO treatment. The δ13C values of the coal soot shifted to more negative whereas the δ13C values of the other four biomass-derived soot/char samples became more positive. The data suggested that interpretation of δ13C data for residual BC materials after thermal treatment should be cautious.

Link between black carbon and resistant desorption of PAHs on soil and sediment

The effects of black carbon (BC) on resistant desorption of organic pollutants in soil and sediment were evaluated to further understand the mechanisms for the resistant desorption and to find a more accurate desorption model which can improve risk assessment and management of ubiquitous soil/sediment contamination. A soil and sediment were used to create “combusted” soil/sediment with only BC and no other organic matter remaining by 375°C chemothermal oxidation (CTO-375) method. Polycyclic aromatic hydrocarbons (PAHs) including naphthalene and phenanthrene were used as sorbates, their sorption and desorption by the original soil/sediment (with organic matter and BC), and combusted soil/sediment (only BC) were examined. All sorption isotherms were fitted with linear model and Freundlich model. Sorption isotherms of naphthalene and phenanthrene on the original soil/sediment were almost linear (Freundlich coefficient n = 0.86, 1.00, 0.87, and 0.75), whereas the BC remaining after the soil/sediment combustion showed nonlinear (n = 0.70, 0.48, 0.56, and 0.55) and higher sorption (e.g., KOC = 1.36 × 104 with naphthalene equilibrium solution concentration of 0.001 mg l-1 for combusted soil, one order higher than that for the original sample accordingly). Desorption resistance was observed for both the original and combusted soil/sediment, and the resistant desorption from combusted soil/sediment was much stronger than that from original soil/sediment based on the quantification of desorption hysteresis with thermodynamic index of irreversibility (TII) values (TII = 0.73–0.88). A biphasic desorption isotherm can well describe the resistant desorption for all PAH-sorbent combinations. The BC could have significant effect on desorption of PAHs from soil and sediment, the BC fraction in soils and sediments could be the predominant component responsible for desorption hysteresis. More accurate biphasic desorption models can be used to improve risk assessment and management of ubiquitous soils/sediments contamination by PAHs.

Differentiation of charcoal, soot and diagenetic carbon in soil: Method comparison and perspectives

The various sources of pyrogenic and coalified carbon (black carbon, BC) in soil have considerable structural heterogeneity, making the quantification of BC a challenge. This study was aimed at evaluating the capability of different detection procedures to recover different types of BC from soil. We added defined quantities of urban dust (UD, NIST SRM1649a), diesel particulate matter (DPM, NIST SRM2975), charcoal, lignite, bituminous coal and wood to four topsoil samples. Mixtures were analyzed by way of chemo-thermal oxidation (CTO), thermal gradient oxidation (ThG), the benzene polycarboxylic acid method (BPCA) and mid-infrared spectroscopy (MIRS). CTO returned good quantification of soot BC in the pure DPM, yet the recovery of soot BC from soil was unsatisfactory (18–270%). ThG gave good precision but lower values for pure soot BC. It severely overestimated the BC content for all soil-standard mixtures. The BPCA method gave a low return for soot BC, but for the spiked soil it reliably detected charcoal and coalified C (69–107% avg. recovery) but underestimated soot BC (52–90% recovery of DPM). Linear coherence in specific MIR vibrations was found in one component soil-BC mixtures for each BC type. Applying these standard calibrations to multi-component mixtures allowed detecting charcoal and a quantification of soot BC (88% avg. recovery) via MIRS, but ignored the presence of diagenetic C. We see the greatest potential in differentiating soot from charcoal in soil by employing a combination of chemical and thermal oxidation and MIRS, while the differentiation from diagenetic C is not possible yet.

Testing the resistance of fullerenes to chemothermal oxidation used to isolate soots from environmental samples

We tested the resistance of five different fullerenes (C 60, C 70, C 76/78 mix, and C 84) to chemothermal oxidation at 375 °C (CTO-375), a method that has been used and tested for quantifying black carbon (BC) and CNTs in soils and sediments. C 60 survived CTO-375 the most (50%), while C 70 was the fullerene with the lowest survival rate (<1%). Standard additions of C 60 to soil and sediment reference materials yielded recoveries between 18 and 36%. Although lower than recoveries previously observed for soot and CNTs, these results demonstrate the capability of CTO-375 to partially isolate C 60 from solid environmental matrices. Standard additions of C 70, C 76/78, and C 84 yielded slightly higher survival rates when added to soil and sediment than in their pure form. These results indicate that the mineral matrices of these samples probably had a catalytic effect towards C 60 and a protective effect towards C 70, C 76/78, and C 84 during CTO-375.

Comparison of Elemental Carbon in Lake Sediments Measured by Three Different Methods and 150-Year Pollution History in Eastern China

Concentrations of elemental carbon (EC) were measured in a 150 yr sediment record collected from Lake Chaohu in Anhui Province, eastern China, using three different thermal analytical methods: IMPROVE_A thermal optical reflectance (TOR), STN_thermal optical transmittance (TOT), and chemothermal oxidation (CTO). Distribution patterns for EC concentrations are different among the three methods, most likely due to the operational definition of EC and different temperature treatments prescribed for each method. However, similar profiles were found for high-temperature EC fractions among different methods. Historical soot(TOR) (high-temperature EC fractions measured by the IMPROVE_A TOR method) from Lake Chaohu exhibited stable low concentrations prior to the late 1970s and a sharp increase thereafter, corresponding well with the rapid industrialization of China in the last three decades. This may suggest that high-temperature thermal protocols are suitable for differentiating between soot and other carbon fractions. A similar soot(TOR) record was also obtained from Lake Taihu (~200 km away), suggesting a regional source of soot. The ratio of char(TOR) (low-temperature EC fraction measured by the IMPROVE_A TOR method, after correction for pyrolysis) to soot(TOR) in Lake Chaohu shows an overall decreasing trend, consistent with gradual changes in fuel use from wood burning to increasing fossil fuel combustions. Average higher char(TOR)/soot(TOR) was observed in Lake Taihu than in Lake Chaohu in the past 150 years, consistent with the longer and more extensive industrialization around the Taihu region.