Claudia Kammann

Hydrothermal carbonization of biomass residuals: a comparative review of the chemistry, processes and applications of wet and dry pyrolysis

The carbonization of biomass residuals to char has strong potential to become an environmentally sound conversion process for the production of a wide variety of products. In addition to its traditional use for the production of charcoal and other energy vectors, pyrolysis can produce products for environmental, catalytic, electronic and agricultural applications. As an alternative to dry pyrolysis, the wet pyrolysis process, also known as hydrothermal carbonization, opens up the field of potential feedstocks for char production to a range of nontraditional renewable and plentiful wet agricultural residues and municipal wastes. Its chemistry offers huge potential to influence product characteristics on demand, and produce designer carbon materials. Future uses of these hydrochars may range from innovative materials to soil amelioration, nutrient conservation via intelligent waste stream management and the increase of carbon stock in degraded soils.

Biochar and hydrochar effects on greenhouse gas (carbon dioxide, nitrous oxide, and methane) fluxes from soils.

With a growing world population and global warming, we are challenged to increase food production while reducing greenhouse gas (GHG) emissions. We studied the effects of biochar (BC) and hydrochar (HC) produced via pyrolysis or hydrothermal carbonization, respectively, on GHG fluxes in three laboratory incubation studies. In the first experiment, ryegrass was grown in sandy loam mixed with equal amounts of a nitrogen-rich peanut hull BC, compost, BC+compost, double compost, or no addition (control); wetting-drying cycles and N fertilization were applied. Biochar with or without compost significantly reduced NO emissions and did not change the CH uptake, whereas ryegrass yield was significantly increased. In the second experiment, 0% (control) or 8% (w/w) of BC (peanut hull, maize, wood chip, or charcoal) or 8% HC (beet chips or bark) was mixed into a soil and incubated at 65% water-holding capacity (WHC) for 140 d. Treatments included simulated plowing and N fertilization. All BCs reduced NO emissions by ∼60%. Hydrochars reduced NO emissions only initially but significantly increased them after N fertilization to 302% (HC-beet) and 155% (HC-bark) of the control emissions, respectively. Large HC-associated CO emissions suggested that microbial activity was stimulated and that HC was less stable than BC. In the third experiment, nutrient-rich peanut hull BC addition and incubation over 1.5 yr at high WHCs did not promote NO emissions. However, NO emissions were significantly increased with BC after NHNO addition. In conclusion, BC reduced NO emissions and improved the GHG-to-yield ratio under field-relevant conditions. However, the risk of increased NO emissions with HC addition must be carefully evaluated.

Seasonal variability and mitigation options for N2O emissions from differently managed grasslands

Nitrous oxide emissions were measured from nine plots on an old grassland site near Giessen, Germany. The management regimes of the plots differed in the amount of nitrogen (N) fertilizer applied, in the cutting frequency and in the mean annual ground water table height. Emissions of N2O occurred mainly shortly after fertilization and during freeze-thaw periods. Additional field incubations (in jars) provided evidence that during frost periods N2O emissions as high as 22.000 ng N2O-N kg−1 soil h−1 originated directly from the frozen topsoil. For the highest fertilized plots the freeze-thaw period accounted for 43 and 52% of the total annual N2O emissions. Nitrous oxide emissions tended to increase with increasing N fertilizer application and decreasing water table depth. Furthermore, an increase in the number of cuttings per year reduced N2O emissions. The results suggest that the ability of plant roots to take up NO3− increases with increased cutting frequencies throughout the vegetation period, therefore reducing the amount of NO3− available for soil denitrifying microorganisms.

Plant growth improvement mediated by nitrate capture in co-composted biochar

Soil amendment with pyrogenic carbon (biochar) is discussed as strategy to improve soil fertility to enable economic plus environmental benefits. In temperate soils, however, the use of pure biochar mostly has moderately-negative to -positive yield effects. Here we demonstrate that co-composting considerably promoted biochars’ positive effects, largely by nitrate (nutrient) capture and delivery. In a full-factorial growth study with Chenopodium quinoa, biomass yield increased up to 305% in a sandy-poor soil amended with 2% (w/w) co-composted biochar (BCcomp). Conversely, addition of 2% (w/w) untreated biochar (BCpure) decreased the biomass to 60% of the control. Growth-promoting (BCcomp) as well as growth-reducing (BCpure) effects were more pronounced at lower nutrient-supply levels. Electro-ultra filtration and sequential biochar-particle washing revealed that co-composted biochar was nutrient-enriched, particularly with the anions nitrate and phosphate. The captured nitrate in BCcomp was (1) only partly detectable with standard methods, (2) largely protected against leaching, (3) partly plant-available, and (4) did not stimulate N2O emissions. We hypothesize that surface ageing plus non-conventional ion-water bonding in micro- and nano-pores promoted nitrate capture in biochar particles. Amending (N-rich) bio-waste with biochar may enhance its agronomic value and reduce nutrient losses from bio-wastes and agricultural soils.

Simple Biotoxicity Tests for Evaluation of Carbonaceous Soil Additives: Establishment and Reproducibility of Four Test Procedures

Biochar derived from pyrolysis has received much attention recently as a soil additive to sequester carbon and increase soil fertility. Hydrochar, a brown, coal-like substance produced via hydrothermal carbonization, has also been suggested as a beneficial soil additive. However, before soil application, both types of char need to be tested for potential toxic effects. The aim of this study was to develop simple, inexpensive, and easy-to-apply test procedures to identify negative effects of chars but not to provide false-negative results. The following tests, based partly on ISO norm biotoxicity test procedures, were chosen: (i) cress germination test for gaseous phytotoxic emissions; (ii) barley germination and growth test; (iii) salad germination test; and (iv) earthworm avoidance test for toxic substances. Test reproducibility was ensured by carrying out each test procedure three times with the same biochar. Several modifications were necessary to adapt the tests for biochars/hydrochars. The tested biochar did not induce negative effects in any of the tests. In contrast, the beet-root chip hydrochar showed negative effects in all tests. In an extension to the regular procedure, a regrowth of the harvested barley shoots without further nutrient additions yielded positive results for the hydrochar, which initially had negative effects. This implies that the harmful substance(s) must have been degraded or they were water soluble and leached. Tests with a biochar and hydrochar showed that the proposed modified quick-check test procedures provide a fast assessment of risks and effects of char application to soils within a short period of time (<2 wk).

Activity and community structure of methane-oxidising bacteria in a wet meadow soil

The structure and activity of the methane-oxidising microbial community in a wet meadow soil in Germany were investigated using biogeochemical, cultivation, and molecular fingerprinting techniques. Both methane from the atmosphere and methane produced in anaerobic subsurface soil were oxidised. The specific affinity (first-order rate constant) for methane consumption was highest in the top 20 cm of soil and the apparent half-saturation constant was 137-300 nM CH(4), a value intermediate to measured values in wetland soils versus well-aerated upland soils. Most-probable-number (MPN) counting of methane-oxidising bacteria followed by isolation and characterisation of strains from the highest positive dilution steps suggested that the most abundant member of the methane-oxidising community was a Methylocystis strain (10(5)-10(7) cells g(-1) d.w. soil). Calculations based on kinetic data suggested that this cell density was sufficient to account for the observed methane oxidation activity in the soil. DNA extraction directly from the same soil samples, followed by PCR amplification and comparative sequence analyses of the pmoA gene, also detected Methylocystis. However, molecular community fingerprinting analyses revealed a more diverse and dynamic picture of the methane-oxidising community. Retrieved pmoA sequences included, besides those closely related to Methylocystis spp., others related to the genera Methylomicrobium and Methylocapsa, and there were differences across samples which were not evident in MPN analyses.

Methane fluxes from differentially managed grassland study plots: the important role of CH4 oxidation in grassland with a high potential for CH4 production

Methane oxidation fluxes were monitored with the closed chamber method in eight treatment plots on a semi-wet grassland site near Giessen, Germany. The management regimes differed in the amount of nitrogen (NH4NO3) fertilizer applied and in the height of the in-ground water table. No inhibition of CH4 oxidation occurred, regardless of the amount of annual N fertilizer applied. Instead, the mean CH4 consumption rates were correlated with the mean soil moisture of the plots. However, the correlation between daily soil water content and corresponding CH4 oxidation rate was always weak. During drought period (late summer) water stress was observed to restrict CH4 oxidation rates. The findings led to the question whether methane production with soil depth might modify the CH4 fluxes measured at the surface. Therefore, two new methods were applied: (1) soil air sampling with silicone probes; and (2) anaerobic incubations of soil cores to test for the methane production potential of the grassland soil. The probe measurements revealed that the CH4 sink capacity of a specific site was related to the vertical length of its CH4 oxidizing column, i.e. the depth of the CH4 producing horizon. Anaerobically incubated soil cores produced large amounts of CH4 comparable with tropical rice paddy soil. Under field conditions, heavy autumnal rain in 1998 led to a dramatic increase of soil CH4 concentrations upto 51 microliters l-1 at a depth of 5 cm. Nevertheless, no CH4 was released when soil surface CH4 fluxes were measured simultaneously. The results thus demonstrate the high CH4 oxidation potential of the thin aerobic topsoil horizon in a non-aquatic ecosystem.

Evidence for methane production by saprotrophic fungi

Methane in the biosphere is mainly produced by prokaryotic methanogenic archaea, biomass burning, coal and oil extraction, and to a lesser extent by eukaryotic plants. Here we demonstrate that saprotrophic fungi produce methane without the involvement of methanogenic archaea. Fluorescence in situ hybridization, confocal laser-scanning microscopy and quantitative real-time PCR confirm no contribution from microbial contamination or endosymbionts. Our results suggest a common methane formation pathway in fungal cells under aerobic conditions and thus identify fungi as another source of methane in the environment. Stable carbon isotope labelling experiments reveal methionine as a precursor of methane in fungi. These findings of an aerobic fungus-derived methane formation pathway open another avenue in methane research and will further assist with current efforts in the identification of the processes involved and their ecological implications.

Biochar reduces copper toxicity in Chenopodium quinoa Willd. In a sandy soil.

Mining, smelting, land applications of sewage sludge, the use of fungicides containing copper (Cu), and other human activities have led to widespread soil enrichment and contamination with Cu and potentially toxic conditions. Biochar (BC) can adsorb several substances, ranging from herbicides to plant-inhibiting allelochemicals. However, the range of potential beneficial effects on early-stage plant growth with regard to heavy metal toxicity is largely unexplored. We investigated the ameliorating properties of a forestry-residue BC under Cu toxicity conditions on early plant growth. Young quinoa plants () were grown in the greenhouse in the presence of 0, 2, and 4% BC application (w/w) added to a sandy soil with 0, 50, or 200 μg g Cu supplied. The plants without BC showed severe stress symptoms and reduced growth shortly after Cu application of 50 μg g and died at 200 μg Cu g. Increasing BC concentrations in the growth medium significantly increased the plant performance without Cu toxicity or under Cu stress. At the 4% BC application rate, the plants with 200 μg g Cu almost reached the same biomass as in the control treatment. In the presence of BC, less Cu entered the plant tissues, which had reduced Cu concentrations in the order roots, shoots, leaves. The amelioration effect also was reflected in the plant-soil system CO gas exchange, which showed clear signs of improvement with BC presence. The most likely ameliorating mechanisms were adsorption of Cu to negatively charged BC surfaces and an improvement of the water supply. Overall, BC seems to be a beneficial amendment with the potential to ameliorate Cu toxicity in sandy soils. Further research with a broad spectrum of different soil types, BCs, and crop plants is required.

Genotoxic and phytotoxic risk assessment of fresh and treated hydrochar from hydrothermal carbonization compared to biochar from pyrolysis

Biochar is discussed as an option for climate change mitigation via C sequestration and may promote sustainable resource efficiency. Large-scale field trials and commercial business with char materials have already started. Therefore char materials have to be assessed for toxic compounds. We tested genotoxic effects of different hydrochars and biochars with the Tradescantia micronucleus test. For this purpose chromosomal aberrations in pollen cells of Tradescantia in the form of micronuclei were evaluated microscopically after defined exposition to extracts from char materials. Hydrochars from hydrothermal carbonization mostly exhibited significantly negative results. Additional germination experiments with hydrochar showed total germination inhibition at additions above five percent v/v in comparison to biochar. However, biological post-treatment of previously toxic hydrochar was successful and toxic effects were eliminated completely. Some post-treated hydrochars even showed growth stimulating effects. Our results clearly demonstrate the necessity of risk assessment with bioindicators. The chosen tests procedures can contribute to biochar and hydrochar characterization for safe application.