Effects of Water-Washed Biochar on Soil Properties

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AUTHOR QUERY FORM JOURNAL: CLEAN – SOIL, AIR, WATER Article: clen201700143 Dear Author, During the copyediting of your manuscript the following queries arose. Please refer to the query reference callout numbers in the page proofs and respond to each by marking the necessary comments using the PDF annotation tools. Please remember illegible or unclear comments and corrections may delay publication.

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Please provide the highest academic title for each author (either Prof. or Dr.) excluding Shengmao Yang.

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National Natural Science Foundation of China

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RESEARCH PAPER Soil

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HaohaoQ1 LuQ2, Yaofeng Wang, Yuxue Liu, Yuying Wang, Lili He, Zheke Zhong, and Shengmao Yang* manure, and crop residues, in the partial or total absence of oxygen (O).[1] Biochar has recently attracted considerable attention due to its ability to improve soil quality and mitigate climate changes.[2,3] Previous studies have shown that soil CH4 emissions were either increased[4–9] or decreased after biochar application.[10–15] Similarly, N2O emissions might be increased or decreased after biochar application with variations in pyrolysis conditions and feedstock.[16,17] Dissolved organic C, which is a small proportion of soil organic matter (SOM), is one of the most mobile and active C pools and thus, plays an important role in the global C cycle and microbial biomass N content in soil ecosystems.[47] DOC is the most important water-soluble organic compound of biochar, which is affected by pyrolysis temperature and feedstock content.[18] Zimmermann et al. indicated that biochar had approximately 7–9% biodegradability and can release as CO2 from the surface.[19] Singla and Inubushi[9] showed that biochar application significantly increase CH4 emission possibly due to affecting the availability of organic C in the soil to microbial activity for methanogenesis. Mineral ash is also an important water-soluble organic compound of biochar, which is significantly positively correlated with soil pH and electrical conductivity. It is well known that soil pH is one of the most important factors that affect N2O and CH4 emissions.[17,20] High feedstock mineral ash content can also lead to the production of relatively high DOC content, particularly of waterextractable organic C (WEOC) content.[21] Besides the water-soluble compound of biochar, there is ample evidence that biochar improves soil physical qualities. Greater aeration and water holding capacity, due to the porosity of biochar, are also important factors that affect N2O and CH4 emissions.[22–24] Hence, we conjecture that previous divergent results may be due to the combined effect of soluble components of biochar and the stable properties of biochar. Moreover, we hypothesize that the stable properties of biochar play a vital role in soil greenhouse gas emission. However, the potential of stable properties for biochar for mitigating climatic impacts is not well established. In this study, a rice pot experiment was performed using bamboo biochar and water-washed bamboo biochar to

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1. Introduction

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Biochar, a carbon (C)-rich solid material, is manufactured by the pyrolysis of plant-derived biomass, such as grass, wood, dairy

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Biochar application might be a newly agricultural method for improving soil quality and carbon sequestration by its special physical and chemical properties which has generated great interest for scientists and policy makers. However, the physical structure of biochar and its effect on N2O and CH4 emissions are not yet clear. The effect of bamboo biochar and water-washed bamboo biochar with or without N fertilization on greenhouse gas emissions, soil properties, and rice yield in a pot experiment are investigated. The results show that biochar application increased soil pH, total N content, dissolved organic carbon (DOC), and rice plant growth. Although biochar application increase DOC  content, N2O and CH4 emissions decrease. The soil NHþ 4 and NO3 contents are significantly decreased by biochar application indicating that bamboo  biochar has a remarkable ability to absorb NHþ 4 and NO3 . However, no significant differences of N2O emission are observed between biochar and washed biochar treatment. The CH4 emission in the washed biochar treatment is decreased to a greater extent than in the unwashed biochar indicating that washed biochar has a greater inhibitory effect on CH4 emission than did unwashed biochar, and that the stable physical structure of biochar might be an important factor for reducing CH4 emissions. Additional studies are needed to investigate the role of functional microorganism in order to better understand the biochar on greenhouse gas emissions from paddy soils.

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Effects of Water-Washed Biochar on Soil Properties, Greenhouse Gas Emissions, and Rice Yield

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H. Lu, Y. Wang, Y. Liu, Y. Wang, L. He, Prof. S. Yang Institute of Environment, Resource, Soil, and Fertilizer Zhejiang Academy of Agricultural Sciences 198 Shiqiao Road, Hangzhou 310021, China E-mail: [email protected] H. Lu, Y. Liu, Y. Wang, L. He, Z. Zhong, Prof. S. Yang Biochar Engineering Research Center of Zhejiang Province Hangzhou, China Y. Wang, Prof. S. Yang Institute of Resource, Ecosystem, and Environment of Agriculture Nanjing Agricultural University Nanjing, China Z. Zhong China National Bamboo Research Center Hangzhou, China

DOI: 10.1002/clen.201700143

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Top soil samples from a depth of 0–20 cm were collected in January 10, 2014 from a percogenic paddy field (yellow loamy paddy soil genus) with typical rice–rape crop rotation located in the Yangdu Haining Agroecological Experimental Station, Zhejiang Province, China (120 240 2300 E, 30 260 0700 N). The collected soil was air-dried, passed through a 2-mm sieve, and mixed to ensure homogeneity. The chemical properties of paddy soil were as follows: pH 6.03 (soil/H2O, 1:2.5); 10.5 g kg1 SOM, 0.08% total N, 0.07% total P, 0.50% total K, 24.3 mg kg1 available P, 71.0 mg kg1 available K, and 167.0 mg kg1 DOC. In this study, biochar was produced from bamboo biomass by pyrolysis at 600  C under N-gas flushing environment for 3 h, and the product was passed through a 2-mm sieve. Washed bamboo biochar was obtained by washing bamboo biochar with distilled water at a ratio of 3:1. Washing was repeated at least five times until the DOC content was 5.9, which might have little effect on N2O emissions among all treatments. WFPS also highly affect N2O emissions with the highest at 83% WFPS, whereas a significant reduction occurs at 73–78% WFPS.[26] Another study also showed that biochar application with N fertilizer significantly enhanced N2O emission at 80%

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Figure 2. Effects of bamboo biochar and washed bamboo biochar with or without N fertilization on rice straw and grain yield. Different letters indicate significant differences at p < 0.05 (n ¼ 4).

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WFPS and waterlogged condition did not affect N2O emissions.[28] In the present study, soil in all treatments was under saturated water holding capacity. Since WFPS might have little effect on N2O emissions among all treatments.  Moreover, soil NHþ 4 and NO3 concentration might affect [25] [29] N2O emissions. Singh et al. reported that wood biochar decreased N2O emissions, which were mainly related to soil  þ NHþ 4 and NO3 , because the absorbance of soil NH4 led to reduced inorganic-N levels. Nitrate N concentration may be an important indicator of nitrification, and it is possible that biochar application decreases N2O emissions from soil due to N immobilization; therefore, biochar addition may decline nitrification and ammonification in the short term.[30] Similarly,  the results showed that soil NHþ 4 and NO3 contents were significantly decreased by biochar application at 1–2 DAT, indicating that bamboo biochar might have a remarkable ability  to absorb NHþ 4 and NO3 . In addition, the physical structure of biochar (higher BET value, porous structure) might be related to differences in N2O emissions. Zhang et al.[4] reported that the stable part of biochar decreased N2O emissions. The process of nitrification and denitrification directly influenced N2O emissions, and the physical structure of biochar such as abundant pore structure pore structure might affect soil microorganism community structure, which is closely associated with N2O emissions.[4] Hence, N2O emissions reduction in  present results might be due to absorption of NHþ 4 and NO3 by biochar and the mechanism of N2O emissions in relation to biochar application should be further investigated using

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4.2. Effects of Biochar and Washed Biochar With or Without N Fertilization on CH4 Emissions

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The impact of biochar application on CH4 emissions remains complex during the previous studies. Han et al.[14] indicated that biochar application could suppress CH4, because of the increased CH4 oxidation activity and pmoA gene abundance of methanotrophs. In contrast, Subedi et al.[5] and Knoblauch et al.[31] reported that biochar application significantly enhanced CH4 emissions. In general, the rate of CH4 emissions in paddy fields mainly depends on soil pH, soil DOC content, water management conditions, physical properties of biochar, and the application rate of N fertilizer.[32–34] Biochar application might influence the activity of methanogens and methanotrophs by changing soil pH. Inubushi et al.[32] suggested that soil pH between 5 and 7.5 can enhance CH4 emissions. CH4 emissions reduction might not be due to pH in the present study. Although the soil pH increased after biochar application, the pH levels in all the six treatments were within the range of 6.2 and 6.8. DOC derived from biochar is considered an important factor that affects soil greenhouse gas emissions when biochar is applied to paddy fields.[9] In general, biochar is thought to be composed of three components: steady C, easily decomposed C, and ash. Unlike SOM, biochar has numerous aromatic carbons and a molten structure. The microbial decomposition of the stable part of C and N in the biochar structure, as well as other elements in biochar, is difficult. However, a small part of easily decomposed C (liable C), which is mineralized and utilized by microorganisms, promotes microbial activity and increases the number of microorganisms.[35,36] Feng et al.[33] indicated that biochar application increased DOC content, which supports methanogen or methanotroph growth. Biochar has been also found to improve microbial C and N, because it allows the soil to absorb many [37,38] organic and inorganic nutrients (NHþ 4 ), particularly DOC. The application of N fertilizer also affects the CH4 emissions in paddy fields. In the present study, CH4 emissions were significantly lower in treatments with N fertilizer than in those without N fertilizer, probably because of the shift in the relationship between CH4 and N2O emissions. N2O emissions in treatment with N fertilizer were higher than those in treatments without N fertilizer. Additionally, it is possible that biochar application adjusts the supply of soil NHþ 4 , and some methanotrophs potentially use NHþ 4 as an energy source and O2 as an electron acceptor.[39] The physical properties of biochar also affect soil CH4 emissions. The porous structure and relatively more internal surface area of biochar are likely to provide a highly specialized habitat for microbes, such as methanogens or methanotrophs, to colonize, grow, and reproduce.[36] Therefore, some studies have indicated that biochar application might decrease CH4 emissions by inhibiting the activity of methanogens[10] or by improving the growth ability of methanotrophs.[14] The results showed that biochar application increased soil DOC, but there was still a significant inhibitory effect on CH4 emissions.

Furthermore, washed biochar, which had no significant effect on soil DOC content compared with the control, significantly increased the inhibitory effect on CH4 emissions. Hence, the stable physical structure of biochar might be the most important factor in reducing CH4 emissions and explain the contradictory results obtained in previous studies. Zimmerman[40] reported that the unstable part of biochar ranged between 5 and 37%, which is considerably higher than the annual biochar mineralization rate that ranges between 2 and 18%. Hence, the application of biochar with a high DOC content might explain the increase in CH4 emissions, whereas the physical properties of biochar such as high surface area or porous structure that strongly inhibit the activity of methanogens might explain the reduction in CH4 emissions.

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4.3. Effects of Biochar and Washed Biochar With or Without N Fertilization on Soil Properties and Rice Yield

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The rice straw and grain yield were improved by biochar application with or without N fertilizer in this study, except for rice grain yield in BB. Biochar probably provides additional nutrients, such as K, Ca, and Mg, and neutralizes soil pH.[41] However, a previous study showed that grain yield decreased after the application of biochar without N fertilization in a soil with poor N availability.[42] Except for the insufficient N supply, the soil type and biochar application rate also affect crop yield.[29,43] In addition, biochar application can improve crop productivity by altering soil properties. In the present study, changes in soil properties, such as soil organic C, pH, and available K, P, and total N, led to increased rice growth, which was in agreement with finding of previous studies.[44,45]

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5. Conclusion

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In the present study, biochar application decreased CH4 and  N2O emissions. Soil NHþ 4 and NO3 content was significantly decreased by biochar application, indicating that such treatment  could remarkably improve NHþ 4 and NO3 absorption by reducing N2O emissions. Biochar application increased soil DOC, pH, and K content, and significantly inhibited CH4 emissions. Contradictory findings with previous studies regarding the impact of biochar application on CH4 emissions could be attributed to the increased CH4 emissions by DOC derived from biochar in combination with the reduced CH4 emissions caused by the physical structure of biochar. In addition, rice straw and grain yield were increased by biochar application with or without N fertilizer. Additional studies, involving methanogens, CH4oxidizing bacteria, and nitrifying or denitrifying bacteria, should be conducted to better understand the effects of biochar application on greenhouse gas emissions.

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Abbreviations

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ANOVA, analysis of variance; BB, bamboo biochar; BBF, bamboo biochar and N fertilizer; BET, Brunauer-Emmett–Teller; CK, control check; CKF, control check and N fertilizer; DAT, days after transplanting; DOC, dissolved organic carbon; ECD,

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electron capture detector; FID, flame ionization detector; SOM, soil organic matter; WB, washed bamboo biochar; WBF, washed bamboo biochar and N fertilizer; WEOC, water-extractable organic carbon; WFPS, water-filled pore space.

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Supporting Information

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Supporting Information is available from the Wiley Online Library or from the author.

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Acknowledgements

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This study was supported by the National Key Science and Technology Project (2014ZX07101-012) and the Natural Science Foundation of Zhejiang (LY16D010004).

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Conflict of Interest

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The authors declare no conflict of interest.

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Received: March 19, 2017 Revised: August 19, 2017 Published online:

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biochar application, dissolved organic carbon, methane, nitrous oxide, soil quality

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Clean – Soil, Air, Water 2018, 1700143

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© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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RESEARCH PAPER The present study shows that N2O and CH4 emissions decreased by biochar application in paddy soil. The washed biochar has a greater inhibitory effect on CH4 emission than did unwashed biochar, and that the stable physical structure of biochar may be an important factor for reducing CH4 emissions.

Soil H. Lu, Y. Wang, Y. Liu, Y. Wang, L. He, Z. Zhong, S. Yang* ...................... 1700143

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Effects of Water-Washed Biochar on Soil Properties, Greenhouse Gas Emissions, and Rice Yield