Naturwissenschaften (2004) 91:436440 DOI 10.

1007/s00114-004-0550-8

SHORT COMMUNICATION

Myrna J. Simpson Patrick G. Hatcher

Overestimates of black carbon in soils and sediments

Received: 14 October 2003 / Accepted: 29 June 2004 / Published online: 24 July 2004  Springer-Verlag 2004

Abstract Several recent reports suggest that black carbon (BC), which broadly encompasses charcoal, soot, and other forms of pyrogenic carbon, may constitute a significant proportion of the refractory carbon in soil and sedimentary organic matter. BC is a sink for biospheric and atmospheric carbon dioxide, and is intimately tied to the biogeochemical cycling of both carbon and oxygen through its role in organic matter cycling. Additionally, BC may represent a large fraction of the missing carbon sink in global carbon accounting. Here, we demonstrate that documented measurements of BC may be the result of methodological artifacts, which inadvertently overestimate the amount of BC. We found that a widely used thermal oxidative method can create a residue that falls under the operational definition of BC in samples that are relatively BC-free. Moreover, during this procedure, labile organic matter constituents are condensed into pyrogenic carbon, implying that the labile components are present in lesser quantities. These methodological deficiencies are promoting overestimates in the amount of refractory carbon in soil and sedimentary organic matter and may endorse inaccuracies in the rates of carbon fluxes, the mean residence times of terrestrial carbon, and organic matter burial rates in oceanic environments.

Introduction
The apparent ubiquity of black carbon (BC) in the environment has several implications for the global cycling of carbon and oxygen, bearing on organic matter burial rates in marine environments and organic matter mineralization rates in terrestrial environments. BC is a generic term used to describe several forms of pyrogenic carbon that encompasses: soot, charcoal, graphite, and products of incomplete combustion (Goldberg 1985), and is defined based on the method used to measure BC (Schmidt et al. 2001). Based on residues from the combustion of vegetation, the global production of BC has been estimated to be between 50 and 270 Tg year1, with 8090% remaining as residues in terrestrial environments (Kuhlbusch and Crutzen 1995; Suman et al. 1997). Much of the BC that exists in marine sediments has been attributed to atmospheric deposition of soot and, in some areas, fluxes from soil BC which has been remobilized and transported via air or water (Suman et al. 1997). Several investigations that aim to quantify the amount of BC indicate that a significant portion of the total amount of terrestrial and aquatic organic carbon is in the form of BC. For instance, BC has been reported to represent as much as 3045% of the total soil organic carbon (Skjemstad et al. 1996; Schmidt et al. 1999; Glaser et al. 2000), 1565% of marine sedimentary organic carbon (Lim and Cachier 1996; Masiello and Druffel 1998; Middelburg et al. 1999), and 572% of high-molecular-weight dissolved organic carbon (Mannino and Harvey 2004). A standardized, thoroughly tested, and established method of measuring BC does not exist despite the fact that one is desperately needed to improve the accounting of global terrestrial and sedimentary carbon, and carbon fluxes and cycles. Many optical, thermal and chemical methods exist for the isolation and measurement of BC (Schmidt and Noack 2000) but are unable to differentiate between the different forms of BC such as soot or charcoal, and may not be applicable to different varieties of natural organic matter. A recent comparison of popular methods produced BC values that varied over two orders of magnitude for the

M. J. Simpson P. G. Hatcher ()) Department of Chemistry and Environmental Molecular Science Institute, Ohio State University, 100 W. 18th Avenue, Columbus, OH 43210, USA e-mail: hatcher@chemistry.ohio-state.edu Tel.: +1-614-6888799 Fax: +1-614-6885920 Present address: M. J. Simpson, Department of Physical and Environmental Science, Scarborough College, University of Toronto, 1265 Military Trail, Toronto, Ontario, M1C 1A4, Canada

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same sample (Schmidt et al. 2001), suggesting that current methods may be subject to interference from nonpyrogenic organic matter and minerals, and/or may produce residues from non-pyrogenic carbon that fall under the definition of BC. It is speculated that chemical methods, which rely on removing labile organic matter components prior to analysis, are unable to remove physically or chemically protected organic matter, thus producing higher values than the other methods. The thermal oxidation method, which heats the sample in an oxygen-rich atmosphere at 375C for 24 h, also produced relatively high values. After a pretreatment that de-mineralized the sample to minimize mineral-catalyzed condensation reactions, the values for BC were reduced significantly (Schmidt et al. 2001; Gelinas et al. 2001). The thermal oxidation procedure, which has been tested and applied to sediment samples, may not be applicable to other samples. For instance, this method is reported to yield BC values from diatom exudates (Gustafsson et al. 2001), demonstrating that this method may produce BC values for samples that are devoid of pyrogenic carbon. Consequently, some published BC values may not be indicative of true BC contents and it is speculated that many of the BC values published to date are dubious (Derenne and Largeau 2001) and do not represent this component of the refractory carbon pool. Some BC methods are commonly applied without rigorous testing and do not consider the inherent variation of natural organic matter samples. As a result, individual results vary widely, depending on the source of the sample and the method used. Methods that employ thermal oxidation assume that labile or non-pyrogenic carbon will not be transformed into what appears to be pyrogenic or BC. Here, we demonstrate with solid-state nuclear magnetic resonance (NMR) spectroscopy, which provides structural information and can confirm the presence or absence of BC, that thermal methods can produce elevated BC values. Accordingly, the application of this method to a wide range of natural organic matter samples can result in overestimates of BC in soils and sediments.

Chemical oxidation was carried out by the method of Simpson and Hatcher (2004). Thermal oxidation was performed by heating the sample at 375C for 24 h in the presence of oxygen (Gustafsson et al. 1997). Solid-state cross polarization (CP) 13C and direct 13C (Bloch decay), both with magic-angle spinning (MAS), NMR spectra were acquired as outlined in Simpson and Hatcher (2004). BC contents are determined from the relative amount of aromatic carbon (aromatic signal at 110140 ppm in solid-state 13C NMR) and the amount of organic carbon left in the sample after chemical oxidation. The fraction of total organic carbon in the form of BC is obtained by dividing the BC content by the total organic carbon content.

Results and discussion

It has been noted that conventional CPMAS 13C NMR, where carbon detection depends on the proximity of neighboring protons, may not be suitable for truly condensed systems such as BC (Hedges et al. 2000). Comparisons of direct and CP detection of naturally charred materials resulted in comparable NMR spectra, indicating that the CP method can be employed in routine analysis (Gelinas et al. 2001; Skjemstad et al. 1999; Skjemstad and Taylor 1999) and indicate that CPMAS data provide good estimates of BC values. However, it should be noted that poor CP efficiencies may result in an underestimation of BC. The ramp-CP method applied here provides good estimates of a mixture of charred wood and cellulose (Simpson and Hatcher 2004). Nonetheless, the accuracy of estimation may vary with the nature of the BC, and the NMR-based values presented here should be used as semi-quantitative estimates of BC. One of the major challenges associated with applying NMR to the determination of BC is the signal overlap from other constituents found in organic matter, namely those arising from lignin. BC components will produce a sharp signal at approximately 130 ppm and lignin will yield signals at 55, 130, and 150 ppm. Although this may not be problematic for all samples, it is certainly challenging for delineating the proportion of aromaticity that arises from BC versus that of lignin and other non-pyrogenic aromatics. It is estimated that as much as 90% of all forest fire residues remain in terrestrial environments (Suman et al. 1997); therefore it is necessary to determine the contribution of BC to the overall soil aromaticity. The solid-state NMR spectra of the charred wood sample are displayed in Fig. 1. This charred wood sample was buried and can be dated back to the eruption of Mount Vesuvius in 79 AD (Hatcher 2002). The top two spectra were acquired using Bloch-decay MAS 13C and CPMAS 13C NMR, respectively, and produced comparable spectra. Both Bloch-decay and CPMAS 13C spectra indicate that some lignin survived the charring process, as a shoulder from a phenolic group, or O-substituted aromatic carbon, is apparent at 150 ppm. After chemical oxidation, this shoulder is no longer detected, indicating that the chemical oxidation method is able to remove residues containing O-substituted aromatic carbon (lignin) from ancient char. On-line pyrolysis gas chromatography mass spectrometry (GC-MS) was also employed

Materials and methods

Soils, sediments, peats, coals, shales, and kerogens were examined by solid-state NMR both before and after chemical oxidation; however, only data for selected samples are highlighted here. A humic acid was isolated from a Florida peat sample (International Humic Substances Society) by the conventional base extraction procedure (Swift 1996). The German and Australian soil samples, which are part of the Standard Collection for BC, were obtained from Dr. Jan Skjemstad at CSIRO Land and Water. A buried, charred wood sample associated with the 79 AD eruption of Mount Vesuvius was collected from Pompeii, Italy. The chemical oxidation data for the following samples are also presented: a surface soil sampled at the Ellerslie Research Station in Edmonton, Canada; a coastal sediment obtained from Pensacola, Florida; a coalified wood sampled from the Morwell open pit mine in Victoria, Australia; and an activated carbon sample purchased from Sigma-Aldrich Chemicals. Chemical oxidation was employed to selectively remove lignin along with other structures found in natural organic matter.

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Fig. 1 A comparison of solid-state NMR methods for an ancient char from the eruption of Mt. Vesuvius in Pompeii. Both direct detection (Bloch-decay MAS) and CPMAS 13C NMR produce similar spectra. After chemical oxidation, residual lignin is removed leaving behind only non-oxidizable aromatic carbon

Fig. 2 Solid-state NMR spectra of a peat humic acid. After chemical oxidation, the aromatic signal (110145 ppm) is diminished, suggesting that this sample contains very little black carbon (BC). Thermal oxidation produces a residue from non-pyrogenic carbon, indicating that this method produces pyrogenic residues from the labile components of relatively BC-free samples

to examine the efficacy of lignin removal in the charred wood sample (M.J. Simpson and P.G. Hatcher, unpublished data). Prior to chemical oxidation, 2-methoxy phenol, a lignin-derived pyrolyzate, was prominent. After chemical oxidation, 2-methoxy phenol was no longer detected, providing further evidence regarding the efficiency of the chemical oxidation method. A large proportion of the aromatic components were removed from the peat humic acid after chemical oxidation (Fig. 2). The relative proportion of the aromatic signal decreased from 24% to 8%, thus yielding a BC content of 0.63%. Signals from lignin and carbohydrates (5072 ppm region) diminished with chemical oxidation. Paraffinic carbon (3032 ppm) survived the treatment, along with non-oxidizable aromatic components. The BC content of the peat humic acid was also evaluated by thermal oxidation using the method outlined by Gustafsson et al. (1997) and the residue was examined by solidstate 13C NMR (Fig. 2). After thermal oxidation, the peat humic acid, a product of extensive biodegradation of plant residues in wetland environments, produces a sample that is highly aromatic with strong signals in the unsubstituted aromatic (120140 ppm) and oxygen-substituted aromatic regions (145165 ppm). After thermal alteration, the sample is free of substantial amounts of carbohydrates and proteins, compounds that are suspected to be responsible for the formation of artifacts during the thermal oxidation treatment. From thermal oxidation, the yield of BC in the peat humic acid is 4.5% (of the total organic carbon) a value that is seven times higher than that obtained from chemical oxidation. The material produced by thermal oxidation could not be oxidized further chemi-

cally, indicating that thermal oxidation of a relatively BCfree material creates a seemingly pyrogenic residue that falls under the broad definition of BC and is resistant to subsequent oxidation. To the best of our knowledge, there are several variations of the thermal oxidation method, which are widely used, although they are not supported by the NMR data for the residues (Gustafsson et al. 1997, 2001; Middelburg et al. 1999; Mannino and Harvey 2004; Kuhlbusch 1995). Although the application of solid-state 13 C NMR to examine natural organic matter is not new, here we demonstrate that 13C NMR provides direct evidence that non-pyrogenic carbon is transformed to BC during thermal oxidation, even though the sample does not contain the types of substances shown to yield thermal artifacts. Ultra-violet (UV) photo-oxidation coupled with solidstate 13C NMR spectroscopy is the result of pioneering work by Skjemstad and co-workers (Skjemstad et al. 1996, 1999; Skjemstad and Taylor 1999). This method removes lignin and other interfering compounds by UV photo-oxidation and then estimates the amount of BC using solidstate 13C NMR. The BC values obtained with this method are higher than those obtained with the chemical oxidation method (Table 1). The UV photo-oxidation method may not be able to access regions of photo-protected lignin within the soil sample (Hedges and Keil 1995), and consequently the measurements by NMR may encompass some signal overlap from lignin. However, efforts to reduce the overlap from protected aromatic components to reduce this possibility are performed by employing a lignin correction factor (Skjemstad and Taylor 1999). The

439 Table 1 Comparison of black carbon (BC) values from different methods. BC values for select samples determined by the chemical oxidation and solid-state NMR method are also listed Sample Australian Vertisolic soil German Mollisolic soil Canadian Chernozemic soil Peat humic material Pompeii charred wood Coastal sediment Brown coal Activated carbon
a c b

Total organic carbon (TOC) (gC/100 g) 3.5 1.9 5.2 55.2 56.7 2.8 61.1 91.5

Oxidative methods (gBC/100 g) 1.04b 0.47b nd 2.52c nd nd nd nd

Chemical oxidation (gBC/100 g) 0.61 0.30 1.16 0.35 33.9 0.19 0 91.0

BC content (% of TOC)a 17.4 15.8 22.3 0.63 59.8 6.8 0 99.5

The percentage of total organic carbon in the form of BC, determined from chemical oxidation and solid-state NMR Determined by UV photo-oxidation and NMR spectroscopy (provided by Dr. J. Skjemstad) Determined by thermal oxidation in this study by the method of Gustafsson et al. (1997) nd, not determined

UV photo-oxidation method may not be as efficient in removing non-pyrogenic carbon prior to NMR analysis, or the chemical oxidation method may be isolating different BC components (Table 1). The BC values obtained with the chemical oxidation method are lower than those values obtained with UV photo-oxidation. However, unlike the thermal oxidative method, both the UV photo-oxidation and chemical oxidation methods do not produce artifacts during the analysis. These varying results should be the focus of future investigations. Demineralization prior to thermal oxidation yields values of BC that are up to three order of magnitudes lower than for samples which have not been demineralized (Gelinas et al. 2001). We acknowledge that this is a possibility and expect that demineralization of the soil and sediment samples used in this study prior to chemical oxidation may contribute to even lower estimates of BC contents than those listed in Table 1. However, the peat humic acid sample is mineral-free, and consequently, minerals could not enhance the transformation of nonpyrogenic carbon to BC. Furthermore, the transformation of non-pyrogenic and labile carbon may be more prolific in mineral-rich samples than observed with the peat humic acid sample and further highlights fundamental problems with thermal oxidative methods. In some reports, BC is arguably an artifact of measurement and is operationally defined based on the type of measurement. Individual methods are liable to different interferences and isolate various components within the BC consortium, and this may explain the disparity amongst published values, as emphasized recently by Schmidt et al. (2001). However, the evidence presented here indicates that thermal oxidative methods will overestimate the amount of pyrogenic carbon and these values must be reconsidered and carefully scrutinized. Furthermore, the amount of pyrogenic carbon formed during the thermal oxidation from labile carbon will lead to underestimations of labile organic matter. Current methods need to be improved such that accurate quantities of BC in the environment can be obtained.

Acknowledgements We thank Dr. J. Skjemstad for providing the Australian and German soil samples and the BC values determined by UV photo-oxidation and solid-state NMR. This research was supported by the National Science Foundation, Environmental Molecular Science Institute (CHE-0089147) and a postdoctoral fellowship to M.J.S. from the Natural Science and Engineering Research Council (NSERC) of Canada.

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