Pyrogenic Organic Matter In Soils Research Articles

Vertical mobility of pyrogenic organic matter in soils: a column experiment

Abstract. Pyrogenic organic matter (PyOM) is a major and persistent component of soil organic matter, but its mobility and cycling in soils is largely unknown. We conducted a column experiment with a topsoil and subsoil of a sand and a sandy loam to study the mobility of highly 13C labeled ryegrass PyOM (>2.8 at. %), applied as a layer on a 7 cm long soil column, under saturated conditions. Further, we used fresh and oxidized PyOM (accelerated aging with H2O2) to identify changes in its migration through the soil with aging and associated surface oxidation. Due to the isotopic signature, we were able to trace the PyOM carbon (PyOM-C) in the soil columns, including density fractions, its effect on native soil organic carbon (nSOC) and its total export in percolates sequentially sampled after 1000–18 000 L m−2. In total, 4 %–11 % of the added PyOM-C was mobilized and <1 % leached from the columns. The majority of PyOM-C was mobilized with the first flush of 1000 L m−2 (51 %–84 % of exported PyOM-C), but its export was ongoing for the sandy soil and the loamy subsoil. Oxidized PyOM showed a 2–7 times higher mobility than fresh PyOM. In addition, 2-fold higher quantities of oxidized PyOM-C were leached from the sandy soil compared to the loamy soil. Besides the higher mobility of oxidized PyOM, its retention in both soils increased due to an increased reactivity of the oxidized PyOM surfaces and enhanced the interaction with the soil mineral phase. Density fractionation of the upper 0–2.3 cm, below the PyOM application layer, revealed that up to 40 % of the migrated PyOM was associated with the mineral phase in the loamy soil, highlighting the importance of mineral interaction for the long-term fate of PyOM in soils. The nSOC export from the sandy soil significantly increased by 48 %–270 % with addition of PyOM compared to the control, while no effect was found for the loamy soil after the whole percolation. Due to its high sorption affinity towards the soil mineral phase, PyOM can mobilize mineral-associated soil organic matter in coarse-textured soils, where organo-mineral interactions are limited, while finer-textured soils have the ability to re-adsorb the mobilized soil organic matter. Our results show that the vertical mobility of PyOM in soils is limited to a small fraction. Aging (oxidation) increases this fraction but also increases the PyOM surface reactivity and thus its long-term retention in soils. Moreover, the migration of PyOM affects the cycling of nSOC in coarse soils and thus influences the carbon cycle of fire-affected soils.

Pyrolysis characteristics of soil humic substances using TG-FTIR-MS combined with kinetic models

The incorporation and cycling of pyrogenic organic matter in soil is a potential carbon sink, while the pyrolysis behaviors of soil organic matter are still lacking. Pyrolysis characteristics of soil fulvic acid (FA) and humic acid (HA) were investigated using thermogravimetry combined with Fourier transform infrared spectrometer-mass spectrometer (TG-FTIR-MS) and kinetic models. Four reaction stages corresponding to four pseudo-components were distinguished for both FA and HA. FA exhibited greater transformation contributions of hemicellulose-like and cellulose-like pseudo-components, while HA exhibited greater transformation contributions of lignin-like pseudo-components. Compared to HA, higher levels of heat-resistant aromatic compounds, phenolic groups, and carboxylic groups were recognized in FA. Values of both activation energy (Ea, 246.13–661.40 kJ·mol−1) and pre-exponential factor (lnA, 53.49–107.16 min−1) of FA were greater than corresponding Ea (241.74–466.70 kJ·mol−1) and lnA (51.99–74.36 min−1) values of HA determined by Flynn-Wall-Ozawa method and Distributed Activation Energy Model. The main pyrolysis reaction mechanisms of both FA and HA closely matched with the order-based model corresponding to 2nd and 3rd order random nucleation on an individual particle. The evolved gas species of H2, CH4, H2O, and CO2 were dominant for FA and HA pyrolysis. Generally, the total H2/CO2 and CH4/H2O releases were relatively larger for FA and HA pyrolysis, respectively. TG-FTIR-MS is shown to be an effective method to provide valuable and qualitative analysis of the gaseous volatile species evolved during HS pyrolysis. Findings from this systematic study of soil organic matter responding to pyrolysis will be critical for predicting the changes of soil systems or carbon cycle affected by future climate and fire regimes.

Carbon losses from pyrolysed and original wood in a forest soil under natural and increased N deposition

Abstract. Pyrogenic organic matter (PyOM) plays an important role as a stable carbon (C) sink in the soils of terrestrial ecosystems. However, uncertainties remain about in situ turnover rates of fire-derived PyOM in soil, the main processes leading to PyOM-C and nitrogen (N) losses from the soil, and the role of N availability on PyOM cycling in soils. We measured PyOM and native soil organic carbon losses from the soil as carbon dioxide and dissolved organic carbon (DOC) using additions of highly 13C-labelled PyOM (2.03 atom %) and its precursor pinewood during 1 year in a temperate forest soil. The field experiment was carried out under ambient and increased mineral N deposition (+60 kg N-NH4NO3 ha−1 year−1). The results showed that after 1 year: (1) 0.5% of PyOM-C and 22% of wood-C were mineralized as CO2, leading to an estimated turnover time of 191 and 4 years, respectively; (2) the quantity of PyOM and wood lost as dissolved organic carbon was negligible (0.0004 ± 0.0003% and 0.022 ± 0.007% of applied-C, respectively); and (3) N additions decreased cumulative PyOM mineralization by 43%, but did not affect cumulative wood mineralization and did not affect the loss of DOC from PyOM or wood. We conclude that mineralization to CO2 was the main process leading to PyOM losses during the first year of mineralization in a forest soil, and that N addition can decrease PyOM-C cycling, while added N showed no effect on wood C cycling.

Biological degradation of pyrogenic organic matter in temperate forest soils

Pyrogenic organic matter (PyOM), derived from the incomplete combustion of plant biomass and fossil fuels, has been considered one of the most stable pools of soil organic matter (SOM) and a potentially important terrestrial sink for atmospheric CO2. Recent evidence suggests that PyOM may degrade faster in soil than previously thought, and can affect native SOM turnover rates. We conducted a six-month laboratory incubation study to better understand the processes controlling the degradation of PyOM in soils using dual-enriched (13C/15N) PyOM and its precursor wood (Pinus ponderosa). We examined the effects of soil type and inorganic N addition on PyOM and wood C and N mineralization rates, microbial C utilization patterns, and native SOM turnover rates. PyOM charred at 450 °C or its precursor pine wood was incubated in two temperate forest subsoils with contrasting short range order (SRO) clay mineralogy (granite versus andesite parent material). Duplicates of experimental treatments with and without PyOM added were sterilized and abiotic C mineralization was quantified. In a second incubation, PyOM or wood was incubated in granitic soil with and without added NH4NO3 (20 kg N ha−1). The fate of 13C/15N-enriched PyOM and wood was followed as soil-respired 13CO2 and total extractable inorganic 15N. The uptake of 13C from PyOM and wood by soil microbial community groups was quantified using 13C-phospholipids fatty acids (PLFA). We found that (1) The mean residence time (MRT) of PyOM-C was on a centennial time scale (390–600 yr) in both soil types; (2) PyOM-C mineralization was mainly biologically mediated; (3) Fungi more actively utilized wood-C than PyOM-C, which was utilized by all bacteria groups, especially gram (+) bacteria in the andesite (AN) soil; (4) PyOM-N mineralization was 2 times greater in granite (GR) than in AN soils; (5) PyOM additions did not affect native soil C or N mineralization rates, microbial biomass, or PLFA-defined microbial community composition in either soil; (6) The addition of N to GR soil had no effect on the MRT of C from PyOM, wood, or native SOM. The centennial scale MRT for PyOM-C was 32 times slower than that for the precursor pine wood-C or native soil C, which is faster than the MRT used in ecosystem models. Our results show that PyOM-C is readily utilized by all heterotrophic microbial groups, and PyOM-C and -N may be more dynamic in soils than previously thought.

Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography–isotope‐ratio mass spectrometry of benzene polycarboxylic acids

Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of δ¹³C values, leading to increased measurement error. Here, we describe a method for δ¹³C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the δ¹³C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1σ). The δ¹³C-BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³C-abundance, produced accurate and precise δ¹³C measurements. Analysis of samples that differed in δ¹³C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ¹³C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ¹³C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways.

Pyrogenic organic matter in soil: Its origin and occurrence, its chemistry and survival in soil environments

Since geological times, vegetation fires have shaped Earth and produced charcoal, which is accumulating in sediments and soils. Only recently the role of pyrogenic organic matter (PyOM) as an important constituent of slow turning soil organic matter (SOM) has received more attention. Whereas in some environments, considerable long residence times of millennia and more were determined for PyOM, newer field and laboratory studies determined turnover times that were in the range of humified fire-unaffected SOM. In order to obtain an explanation of those contradictory observations, a better understanding of the nature of PyOM and its stability in different soil environments is needed. Therefore, after emphasizing the importance of fire and charcoal production during history, the present knowledge about occurrence, chemistry of PyOM formation and its recalcitrance is reviewed in the present work. Summarizing this information, it is revealed that PyOM can be decomposed by physical, chemical and biological means, and that its resistance against degradation in soils largely depends upon its chemistry and the environment in which it is accumulating. Comparable to humification of fire-unaffected SOM, different mechanisms including O 2-deficiency, unfavorable conditions for microorganisms, or interaction with the mineral phase seem to be involved in PyOM preservation and stabilization. Depending on soil conditions, the efficiency of the single pathway varies, resulting in a PyOM pattern which is typical for a certain soil, and it may even represent a typical feature of it. This concept could explain the varying abundance and recalcitrance of PyOM in fire-affected soils, some of which are presented in more detail within this work. In turn, the respective PyOM pattern, which could have been generated over decades and millennia, determines typical soil properties. Thus, PyOM can be seen to be actively involved in the pedogenic process, leading to soil classes such as Terra preta soils in the Amazon region, and possibly also to Chernozems in Central Europe or other Black Soils all over the world.