Towards biochar and hydrochar engineering-influence of process conditions on surface physical and chemical properties, thermal stability, nutrient availability, toxicity and wettability

Dieguez-Alonso A., Funke A., Anca-Couce A., Rombolà A.G., Ojeda G., Bachmann J., Behrendt F. (2018) Towards biochar and hydrochar engineering-influence of process conditions on surface physical and chemical properties, thermal stability, nutrient availability, toxicity and wettability. Energies. 11: 0-0.
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Doi: 10.3390/en11030496

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The impact of conversion process parameters in pyrolysis (maximum temperature, inert gas flow rate) and hydrothermal carbonization (maximum temperature, residence time and post-washing) on biochar and hydrochar properties is investigated. Pine wood (PW) and corn digestate (CD), with low and high inorganic species content respectively, are used as feedstock. CD biochars show lower H/C ratios, thermal recalcitrance and total specific surface area than PW biochars, but higher mesoporosity. CD and PW biochars present higher naphthalene and phenanthrene contents, respectively, which may indicate different reaction pathways. High temperatures (>500 °C) lead to lower PAH (polycyclic aromatic hydrocarbons) content (<12 mg/kg) and higher specific surface area. With increasing process severity the biochars carbon content is also enhanced, as well as the thermal stability. High inert gas flow rates increase the microporosity and wettability of biochars. In hydrochars the high inorganic content favor decarboxylation over dehydration reactions. Hydrochars show mainly mesoporosity, with a higher pore volume but generally lower specific surface area than biochars. Biochars present negligible availability of NO- 3 and NH+ 4 , irrespective of the nitrogen content of the feedstock. For hydrochars, a potential increase in availability ofNO- 3 ,NH+ 4 , PO3- 4 , and K+ with respect to the feedstock is possible. The results from this work can be applied to "engineer" appropriate biochars with respect to soil demands and certification requirements. c 2018 by the authors. Licensee MDPI, Basel, Switzerland. © 2018 by the authors. Licensee MDPI, Basel, Switzerland.

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Are soil-water functions affected by biochar application?

Ojeda G., Mattana S., Avila A., Alcaniz J.M., Volkmann M., Bachmann J. (2015) Are soil-water functions affected by biochar application?. Geoderma. 249-250: 1-11.
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Doi: 10.1016/j.geoderma.2015.02.014

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Today biochar is considered a stable-carbon source that is able to improve soil quality. However, although biochar effects on some soil properties are already becoming well known, its impact on complex soil hydrological functions has yet to be better assessed. The main objectives are: (a) to determine the impact of different biochar amendments on important physical and chemical soil properties and (b) to determine whether the origin (biomass or sewage sludge) and pyrolysis technique can change biochar properties and regulate biochar influence on important soil functions, i.e. nutrient release, water sorption, and carbon storage. Six types of biochar produced from different biomass sources (pine, poplar or sludge) and pyrolysis processes (slow, fast or gasification) were applied to a sandy-loam, low-organic-matter, calcareous soil (mean dose: 18. g/kg) and incubated in a greenhouse without seeding. Two sampling campaigns, one month and one year after biochar amendments, were performed. The overall impact of biochar, analysed by principal response curves (PRCs), indicated that it could improve or deteriorate soil hydrological properties at different intensities. Soil wettability was modified due to sludge biochar addition to soil by increased water penetration dynamics during the capillary rise process of about 18%. In contrast, water storage as a soil function during soil drying was not affected. Because no differences on aggregate stability were observed between treatments, increments on soil organic carbon could not be related to biochar physical protection caused by aggregate formation or by enhanced aggregate stability. As a result, carbon storage, considered as a soil function provided by biochar, was mainly related to its chemical stability. On the other hand, nutrient flux during soil slaking was improved, increasing nutrient release from soil to water. In terms of biochar properties, an increment of surface wettability of biochar during water drop penetration was observed after one year of its addition to soil, where the mean values of contact angle (CA) decreased 69.5%. This important result suggest that initial biochar hydrophobicity (CA. >. 90°) disappeared after 1. year. It was observed that PRC analysis was able to identify important key soil properties that should be monitored when biochar is used as soil amendment. We conclude that the impact of biochar on soil functions depends mainly on biochar feedstock rather than on the pyrolysis technique used during its production. In general, the performance of biochar obtained from sludge and vegetal biomass was markedly different. © 2015 Elsevier B.V.

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Carbon sequestration in a limestone quarry mine soil amended with sewage sludge

Ojeda G., Ortiz O., Medina C.R., Perera I., Alcaniz J.M. (2015) Carbon sequestration in a limestone quarry mine soil amended with sewage sludge. Soil Use and Management. : 0-0.
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Doi: 10.1111/sum.12179

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To reclaim a limestone quarry, 200 and 400 Mg/ha of municipal sewage sludge were mixed with an infertile calcareous substrate and spread as mine soil in 1992. Soil samples were taken 1 week later and again after 17 yr of mine soil rehabilitation so as to assess changes in the amount and persistence of soil organic carbon (SOC). Sludge application increased SOC as a function of the sludge rate at both sampling times. Seventeen years after the sludge amendments, the nonhydrolysable carbon was increased in the 400 Mg/ha of sludge treatment. The recalcitrance of SOC was less in sludge-amended soils than in the control treatment at the initial sampling, but 17 yr later this trend had reversed, showing qualitative changes in soil organic carbon. The CO2-C production had not differed between treatments, yet the percentage of mineralized SOC was less in the high sludge dose. When the size of active (Cactive) and slow (Cslow) potentially mineralizable C pools was calculated by curve fitting of a double-exponential equation, the proportion of Cactive was observed to be smaller in the 400 Mg/ha sludge treatment. Soil aggregate stability, represented by the mean weight diameter of water-stable soil aggregates, was significantly greater in mine soil treated with the high dose of sludge (18.5%) and SOC tended to be concentrated in macro-aggregates (5-2 mm). Results suggest that SOC content in sludge-amended plots was preserved due by (i) replacement of the labile organic carbon of sludge by more stable compounds and (ii) protection of SOC in aggregates. © 2015 British Society of Soil Science.

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Can organic amendments be useful in transforming a mediterranean shrubland into a dehesa?

Tarrason D., Ojeda G., Ortiz O., Alcaniz J.M. (2014) Can organic amendments be useful in transforming a mediterranean shrubland into a dehesa?. Restoration Ecology. 22: 486-494.
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Doi: 10.1111/rec.12092

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Transforming a shrubland into a dehesa system may be useful for recovering certain productive and regulatory functions of ecosystems such as grazing potential, soil erosion control, and also for reducing the risk of wildfire. However, the productivity of the herbaceous cover and tree development in the transformed system may be limited by soil fertility, especially after wildfire events. Previous studies have shown that adequate doses of sewage sludge may improve soil fertility and facilitate plant recovery, but few studies have focused on plant biodiversity assessment. Here, we compare the effects of sewage sludge that has undergone different post-treatments (dewatering, composting, or thermal drying) as a soil amendment used to transform a fire-affected shrubland into a dehesa, on tree growth and pasture composition (vegetation cover, species richness, and diversity). In the short term, sewage sludge causes changes in both pasture cover and tree growth. Although no major differences in vegetation species richness and composition have been detected, fertilization using sewage sludge was shown to modify the functional diversity of the vegetation community. Rapid replacement of shrubs by herbaceous cover and ruderal plants (e.g. Bromus hordeaceus and Leontodon taraxacoides) and of the three grass species sown (Festuca arundinacea, Lolium perenne, and Dactylis glomerata) was observed, whereas N-fixing species (leguminous) tended to be more abundant in nonfertilized soils and soils amended with composted sludge. These results indicate that sewage sludge modifies the functionality of vegetation when applied to soils, and that the response varies according to the treatment that the sludge has undergone. © 2014 Society for Ecological Restoration.

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Effects of nonylphenols on soil microbial activity and water retention

Ojeda G., Patrício J., Navajas H., Comellas L., Alcañiz J.M., Ortiz O., Marks E., Natal-da-Luz T., Sousa J.P. (2013) Effects of nonylphenols on soil microbial activity and water retention. Applied Soil Ecology. 64: 77-83.
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Doi: 10.1016/j.apsoil.2012.10.012

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The main aim of this study is to analyze the influence of 4-nonylphenol (NP) on soil water retention and biological activity. Two doses of 4-nonylphenol (25 and 50mgkg-1) were tested in a loam soil with and without peat amendment. In general, one week after the start of the experiment, the soil water content retained at -0.75MPa of soil suction was 18% higher in the soil amended and its basal respiration (BR) was 15% higher than soil without peat. In contrast, the microbial activity indices (CM: coefficient of mineralization or BR:total organic carbon (TOC) ratio; Cmic:Corg: microbial biomass carbon (MBC):TOC ratio; qCO2: metabolic quotient or BR:MBC ratio) were higher in the soil without peat, compared to the soil amended with peat. On the other hand, the addition of NP to soil was able to modify soil biological but not physical (water retention, desorption) properties. When soil was amended with peat, MBC was reduced one week after applying NP. In contrast, no effects of NP on MBC were observed in the soil without peat. BR was reduced by 16% one week after applying 50mgkg-1 of NP to soil with peat, and was increased by 46% one week after applying 25mgkg-1 of NP to soil without peat. The effects of NP on MBC and BR could be associated more with the adsorption of NP by soil organic matter, while changes in CM or Cmic:Corg ratio were more closely related to changes in soil water retention. The potential toxic effects of NP (high qCO2 values) were only observed in the absence of peat amendments. Peat addition reduced NP toxic effects on microorganisms. © 2012 Elsevier B.V.

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Biochar application on a Mediterranean barley crop could reduce soil CH4, N2O and NH3 emissions

Ribas A, Llurba R, Ojeda G, Mattana S, Debrouk H, Sebastià T, Domene X (2012) Biochar application on a Mediterranean barley crop could reduce soil CH4, N2O and NH3 emissions (Póster) Workshop Biochar as option for sustainable resource management: An European Perspective - EU COST Action TD 1107. 24-25. Chania,

Influencia de las aplicaciones de biochar en cultivo de cebada en las emisiones de gases invernadero

Ribas A, Llurba R, Ojeda R, Ojeda G, Mattana S, Goriveau F, Sebastià T, Domene X (2012) Influencia de las aplicaciones de biochar en cultivo de cebada en las emisiones de gases invernadero (Póster) En: 1st Workshop on Mitigation of GHG Emissions from Spanish Agroforestry Sector (REMEDIA 2012), Bilbao, 8-9 marzo 2012.

Soil biochar amendments: type and dose effects

Ojeda G, Domene X, Mattana S, Sousa JP, Ortiz O, Andrés P, Alcañiz JM (2012) Soil biochar amendments: type and dose effects (Póster). EGU General Assembly. Viena, Austria, 22 -27 April 2012.

Improving substrate fertility to enhance growth and reproductive ability of a Pinus halepensis Mill. afforestation in a restored limestone quarry

Ortiz O., Ojeda G., Espelta J.M., Alcañiz J.M. (2012) Improving substrate fertility to enhance growth and reproductive ability of a Pinus halepensis Mill. afforestation in a restored limestone quarry. New Forests. 43: 365-381.
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Doi: 10.1007/s11056-011-9286-4

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We have evaluated the effects of improving substrate fertility on the growth and reproduction of a P. halepensis plantation in a restored limestone quarry on a stony calcareous regolith (R plots). The natural substrate was supplemented by adding a 0.2 m layer of a fine textured soil (RS plots) or a sewage sludge amended soil (RSS plots). The treatments were performed when the pines were 7 years old, and tree growth (height and trunk and canopy diameter) was monitored over the subsequent 12 years. The reproductive status of the trees was also measured when the pines were 20 years old. Tree growth was proportional to the amount of soil nutrients: 12 years after treatment the mean height of the R, RS and RSS trees was 1.5, 3.1 and 6.2 m respectively and growth increases over the baseline were 76, 264 and 632%. The treatment also affected the age of onset of reproduction (15, 11 and 9 years, respectively), the average number of cones per tree (12, 43 and 61), and the amount of seeds per cone (37, 52 and 72), but did not modify the germination percentage of pine seeds (ca 71.5%). Soil organic carbon increased proportionally to the vegetation development, contributing to carbon sequestration. These results suggest that improving the nutritional status of the soil not only improves the growth of trees, but it also ameliorates their reproductive ability (earlier reproduction onset and larger seed crop size). Implications for soil restoration through afforestation are also discussed. © 2011 Springer Science+Business Media B.V.

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Soil wetting-drying and water-retention properties in a mine-soil treated with composted and thermally-dried sludges

Ojeda G., Mattana S., Bonmatí M., Woche S.K., Bachmann J. (2011) Soil wetting-drying and water-retention properties in a mine-soil treated with composted and thermally-dried sludges. European Journal of Soil Science. 62: 696-708.
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Doi: 10.1111/j.1365-2389.2011.01378.x

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The main objective of this study was to analyse how different sewage sludges influence soil wetting and drying dynamics. Three composted and three thermally-dried municipal sludges from different wastewater plants located in Catalonia (NE Spain) were mixed with a mine-soil obtained from a limestone quarry. Measurements of the time required to reach zero contact angle () and water holding time (WHT) provided information on the time required for a mine-soil to reach its complete wettability and the residence time of water stored between -0.75 and -25 MPa of soil suction, respectively. One month after sludge amendments, one composted and one thermally-dried sludge significantly increased WHT was increased in the mine-soil treated by composted sludges (50.6% by Blanes' sludge, 65.5% by Manresa's sludge and 52.5% by Vilaseca's sludge) one month after sludge amendments. The amount of water retained in the mine-soil was increased by all composted sludges and one thermally-dried sludge after one month (by 42.3% with Blanes' sludge, 42.3% with Manresa's sludge, 65.7% with Vilaseca's sludge and 23.9% with Mataró's sludge) and one year after sludge amendments and at a small suction. Increments in WHT corresponded with the amount of water retained so the time-scale of soil water availability should also be considered. The value was modified mainly by increments in carbon stock and microbial biomass, while the WHT was modified mainly by increments in pH and electrical conductivity. Under similar air-drying conditions, mine-soil treated with composted sludges retained more water for longer compared with thermally-dried sludges. © 2011 The Authors. Journal compilation © 2011 British Society of Soil Science.

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