European Journal of Soil Science, March 2015, 66, 329–338 doi: 10.1111/ejss.12225 Effects of biochar application on greenhouse gas emissions, carbon sequestration and crop growth in coastal saline soil X . W . L i n a,b, Z . B . X i e a, J . Y . Z h e n g b, Q . L i u a, Q . C . B e i a & J . G . Z h u a a State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science, Chinese Academy of Sciences, 71 East Beijing Road, Nanjing 210008, China, and b State Key Laboratory of Soil Erosion and Dryland Farming on the Loess, Institute of Soil and Water Conservation, Chinese Academy of Sciences, 26 Xinong Road, Yangling, 712100, China Summary To evaluate the benefits of application of biochar to coastal saline soil for climate change mitigation, the effects on soil organic carbon (SOC), greenhouse gases (GHGs) and crop yields were investigated. Biochar was applied at 16 t ha−1 to study its effects on crop growth (Experiment I). The effects of biochar (0, 3.2, 16 and 32 t ha−1 ) and corn stalk (7.8 t ha−1 ) on SOC and GHGs were studied using 13 C stable isotope technology and a static chamber method, respectively (Experiment II). Biochar increased grain mass per plant of the wheat by 27.7% and increased SOC without influencing non-biochar SOC. On average, 92.3% of the biochar carbon and 16.8% of corn-stalk carbon were sequestered into the soil within 1 year. The cumulative emissions of CO2 , CH4 and N2 O were not affected significantly by biochar but cornstalk application increased N2 O emissions by 17.5%. The global warming mitigation potential of the biochar treatments (−3.84 to −3.17 t CO2 -eq. ha−1 t−1 C) was greater than that of the corn stalk treatment (−0.11 t CO2 -eq ha−1 t−1 C). These results suggest that biochar application improves saline soil productivity and soil carbon sequestration without increasing GHG emissions. Introduction Soil carbon (C) sequestration through agricultural landmanagement changes is a cost-effective and environmentally friendly strategy for mitigating global warming (Lal, 2004). The incorporation of organic materials into the soil could increase farmland soil organic C (SOC) (Xie et al., 2007). However, organic matter amendment could stimulate methane (CH4 ) emissions in paddy soils and nitrous oxide (N2 O) emissions in some upland soils (Xie et al., 2010; Cheng et al., 2012). Methane and N2 O have 25 and 298 times greater global warming potential (GWP) than carbon dioxide (CO2 ) (Forster et al., 2007). Therefore, improving soil C sequestration and climate change mitigation through residue incorporation into soils should be limited in farmlands when it stimulates GHG emissions (Powlson et al., 2011). Recently, pyrolysis of crop residues in limited oxygen conditions and storage of the pyrolyzed materials (biochar) in soils has been suggested as a possible strategy for soil C sequestration and climate mitigation because of the relative recalcitrance of biochar to microbial decay as a result of its chemical composition and strong aromaticity (Woolf et al., 2010; Lehmann et al., 2011). Some studies have shown that the mean residence time of biochar Correspondence: Z. B. Xie. E-mail: [email protected] Received 6 November 2013; revised version accepted 18 November 2014 © 2015 British Society of Soil Science (hundreds to thousands of years) in soils is greater than that of the soil organic C (tens to hundreds of years), which mostly comes from plant residue incorporation into soil (Hamer et al., 2004; Novak et al., 2010). Therefore, applying biochar to soil will slow the return of photosynthetically fixed C to the atmosphere (Woolf et al., 2010; Lehmann et al., 2011). Moreover, biochar is thought to enhance the climate mitigation potential by offsetting C emissions through the resulting decrease in agricultural fertilizer demand and associated energy expenditure, and improve the terrestrial C sink through the enhancement of crop production with increased soil fertility (Lehmann et al., 2003; Jones et al., 2011). These positive effects have promoted application of biochar to soils as a sustainable management technique for enhancing soil productivity and long-term C storage (Knoblauch et al., 2011). Applying biochar to agricultural soils changes soil properties and microbial activity and populations that could modify the soil C cycle and the non-CO2 GHG fluxes (Lehmann et al., 2003, 2011). However, biochar may be produced from diverse sources with different charring methods and thus its properties and effects on soil processes can vary greatly (Saarnio et al., 2013). Studies on the effects of biochar application on soil CO2 emissions and native SOC are not always consistent, with CO2 emissions and native soil organic C decreasing, increasing or remaining unchanged when different types of biochar are applied to different soils (Novak et al., 2010; Luo et al., 2011; Zimmerman et al., 2011; Troy et al., 2013). 329 330 X. W. Lin et al. Some studies have shown that biochar application decreases soil CH4 and N2 O emissions (Yanai et al., 2007; Spokas & Reicosky, 2009; Yu et al., 2013), whereas other studies have shown that biochar application does not change or even increases soil CH4 and N2 O emissions (Clough et al., 2010; Bruun et al., 2011; Knoblauch et al., 2011; Troy et al., 2013). These differences illustrate the uncertainty regarding the effects of biochar application on the soil C cycle and GHGs when different biochar materials are incorporated into different soils. Therefore, the effects of biochar application on soil C sequestration and GHG emissions should first be investigated to determine its potential for climate change mitigation with a full knowledge of its chemical and physical properties before it is applied to large areas of farmland. Saline soils are widespread throughout the world and occupy about 400 million ha (FAO, 2008). For example, the total area of saline soil is 7 million ha in Europe (mainly in the Mediterranean countries) and 195 million ha in Asia, the Pacific and Australia (FAO, 2008). However, saline soils have smaller SOC concentrations and crop yields than other agricultural soils. For example, the SOC concentration in surface coastal saline soil is 6 g kg−1 , which is only 42% of that of other agricultural soils (Wang et al., 2004). The poor productivity of saline soil because of its large salt content and poor structure and porosity limits further C accumulation. Biochar has large potassium and organic C contents and good porosity. Therefore, applying biochar would hypothetically improve the productivity of saline soil and increase its soil C sequestration and global warming mitigation potential (GWMP). However, there are some uncertainties regarding whether biochar application could improve crop growth and increase GWMP in saline soils when compared with the traditional incorporation of residue into soils. In this study, we developed a field microcosm experiment applying biochar generated from corn stalks and from unmodified corn-stalk residues to saline soil to determine subsequent soil C sequestration and GHG emissions and to compare effects on GWMP. This study specifically aims to (i) investigate the effects of biochar application on crop (soya bean and wheat) growth in a coastal saline soil, (ii) assess the effects of biochar and feedstock application on soil C respiration, soil C sequestration and GHG emissions and (iii) evaluate the GWMP of both materials after biochar or corn stalk application to a coastal saline soil. Materials and methods Study site The experiment was conducted on coastal saline land, located in the east of Yancheng City, Jiangsu Province, China (32∘ 59′ 37.04′′ N, 120∘ 47′ 54.14′′ E; 1 m a.s.l.). The local climate is northern sub-tropical, with an annual mean air temperature of 14.1∘ C, an annual mean precipitation of 1040 mm and approximately 213 frost-free days. The soil is a loamy sand and is classified as a Solonchak according to the USDA and FAO soil classification system (FAO, 1998; Soil Survey Staff, 2006). The average soil salt concentration is 1.5‰ and the average soil bulk density is Table 1 Characteristics of the saline soil and the biochar used in this study Material TOC / g kg−1 TN / g kg−1 TP / g kg−1 TK / g kg−1 C:N pH Soil 6.3 Biochar 685.0 0.4 13.4 0.58 1.5 19.6 13.4 16.0 9.0 51.1 9.6 Soil and biochar pH was measured in a 1:2.5 (soil:water) and 1:20 (biochar:water) mass ratio, respectively. Soil samples were collected from the 0–20-cm depth. TOC, TN, TP and TK refer to total organic C, total nitrogen, total phosphorus and total potassium concentration, respectively. 1.15 g cm−3 at 0–20-cm depth. Other soil chemical properties at 0–20-cm depth are shown in Table 1. Preparation of biochar The biochar was produced from corn (maize) stalks. The stalks were air-dried (10% moisture content), cut into 1-cm pieces, and pyrolyzed in a carbonization furnace (Model ZBX1, Nanjing Nianda Furnace Science and Technology Co. Ltd, Nanjing, China). The furnace was heated to 400∘ C and maintained at this temperature for 4 hours. During pyrolysis, the furnace was filled with N2 at a rate of 0.5 l minute−1 to limit the O2 content. The biochar was cooled overnight after pyrolysis. The biochar was later ground and passed through a 1-mm sieve. The chemical properties of the biochar are shown in Table 1. Microcosm experiments Two microcosm experiments were conducted from June 2010 to June 2011; one focused on crop growth (Experiment I) and the other focused on GHG exchange and SOC dynamics (Experiment II). The microcosms were made from 5 mm-thick high-density polyvinyl chloride (PVC) boards with inner dimensions of 23 × 18 × 20 cm3 (length × width × height; without bases). Soil samples from the 0–20-cm depth were separated from plant debris and roots, and were sieved (< 2 mm) and air-dried. Biochar or corn stalks (cut into 1 cm-long pieces) were mixed well with 9.0 kg air-dried soil samples in each microcosm (packing density: 1.15 g cm−3 ). The microcosms were embedded at 0–20-cm depth in the soil and approximately 50 cm apart. All microcosms were amended with N-P-K (15-15-15) compound fertilizer to give 75.0 kg ha−1 N, 32.8 kg ha−1 P and 62.5 kg ha−1 K during crop production at the seed filling stage of soya bean (on 25th August) and at the growth stage of wheat (on 30th March). Weeds in the microcosms were removed by hand during the investigation. Experiment I. In this experiment, the effect of biochar on crop yields was determined. We developed six microcosms assigned to two treatments, 16 t ha−1 biochar + crops (BC16) and no biochar + crops (Control), each with three replicates and in a completely randomized design. The experiment followed the local soya bean–wheat rotation pattern. Soya bean (Glycine max L., cultivar Huaidou No. 4) was sown in June 2010 and wheat (Triticum aestivum L., cultivar Zhengmai No.9023) was sown in November © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 Biochar’s effects on GHGs, soil C cycle and crop growth 331 2010 after the harvest of the soya bean. Three soya bean plants in the soya bean season and six wheat plants in the wheat season were grown in each microcosm. Soya bean and wheat were harvested in October 2010 and June 2011, respectively. The biomass and grain mass per plant were recorded at harvest. Above-ground biomass was separated into seeds and stalks. Dry mass was determined after drying at 65∘ C for 72 hours. The yield factors of soya bean (number of pods and seeds per plant, and hundred-seed mass) and wheat (number of tillers and seeds per plant, and thousand-grain mass) were also determined. Experiment II. To determine the effects of biochar and corn stalk application on the SOC and GHG fluxes, 15 microcosms (without plants) were assigned to five treatments: control without biochar or corn stalk (Control); 3.2 t ha−1 biochar (BC3.2); 16 t ha−1 biochar (BC16); 32 t ha−1 biochar (BC32); and 7.8 t ha−1 corn stalk (CS). Approximately 3.2 t of biochar was pyrolyzed from 7.8 t corn stalk (the average annual corn stalk biomass per hectare at the study site). This experiment was carried out with three replicates in a completely randomized design. Measurement of greenhouse gas fluxes Fluxes of CO2 , CH4 and N2 O in the 15 microcosms (Experiment II) were measured with opaque static chambers (Conen & Smith, 1998). The static PVC chambers with internal dimensions of 23 × 18 × 50 cm3 (length × width × height) were placed on a water trough on top of the microcosm during air sampling. A fan (10 cm in diameter) was installed on the top wall of each chamber to ensure mixing of gas samples when the chamber was closed. Thermal insulation materials and aluminum film were added to the exterior of the PVC cover to reduce the effects of direct radiative heating during sampling. Generally, GHG samples were measured every 7–14 days during spring, summer and autumn and once a month in winter. From 09.00 to 11.00 local time, a 20-ml gas sample was collected with plastic syringes at 0, 15 and 30 minutes after chamber closure. The samples were transferred to evacuated 15-ml vials (Nichiden–Rika Glass Co. Ltd, Kobe, Japan). Carbon dioxide and methane concentrations were measured with a gas chromatograph (CP 3380, Varian, Palo Alto, CA, USA) with an electron capture detector. Flux rates were calculated from the linear increase in CO2 , CH4 and N2 O concentrations in the chamber headspace over 30 minutes. Cumulative emissions of GHGs were estimated as the summation of daily GHG fluxes obtained through linear interpolation between sampling dates throughout the whole experimental period. Soil environmental variables and chemical analysis Soil temperature at 5-cm depth at the experimental site was measured with digital thermometers when gas samples were collected in the field. The volumetric soil moisture (%) was measured in the microcosms by time domain reflectometry (TDR, Mpkit-B, Beijing Channel Scientific Instruments Co. Ltd, Beijing, China). Soils were sampled (0–20 cm) in microcosms with an auger at the end of the GHG investigation. Soil samples, with the plant debris and roots removed by hand, were sieved (< 2 mm) and air-dried. The SOC content was determined by the Walkley–Black procedure (Walkley & Black, 1934), which consists of dichromate and sulphuric acid digestion and ferrous sulphate titration. Soil pH was determined in water at a soil:water ratio of 1:2.5 using a combination electrode (Rayment & Lyons, 2011). Soil salinity was determined by measuring the electrical conductivity of the extracts (1:5 soil:water mass ratio) with a conductivity meter. Exchangeable cations (K+ , Na+ , Ca2+ and Mg2+ ) in the soil samples were determined after extracting 20 g in 100 ml ammonium acetate (1 m) and then analysing the extracts by inductively coupled plasma atomic emission spectroscopy (ICP–AES, PerkinElmer Optima 8000, Perkin Elmer, Waltham, USA). Estimation of the global warming mitigation potential The saline soil in our study site had a 𝛿 13 C of −22.72‰, because it had been planted with C3 plants for 9 years (hereafter referred to as C3 soil). Maize (corn) is a C4 plant with a 𝛿 13 C of −12.07‰; corn biochar has a 𝛿 13 C of −13.08‰. Therefore, we estimated the SOC contributed by the C4 materials (corn biochar and corn stalk) to the soil samples by using the stable isotope technique. Carbonate in soil samples was removed with 10% HCl, samples were washed with deionized water and dried overnight (80∘ C) and the 𝛿 13 C values were determined by isotope ratio mass spectrometry (MAT 251, Finnigan, Bremen, Germany). The SOC fractions from the biochar or the corn stalks were calculated as follows: ( 13 ) 𝛿 CA+B − 𝛿 13 CA F= ( (1) ) , 𝛿 13 CB − 𝛿 13 CA where F is the proportion of C from C4 , and 𝛿 13 CA , 𝛿 13 CB and 𝛿 13 CA+B are the 𝛿 13 C values of the corresponding control soil, the biochar/corn stalk material and the soil samples in the biochar/corn stalk microcosms, respectively. The amount of C sequestration derived from C4 sources (biochar/corn stalk) in soil samples (SB ) was as follows: SB = SA+B × F, (2) where SA+B is the amount of C in the microcosms and F is the proportion of C from C4 sources. The global warming potential (GWP) of non-CO2 greenhouse gases in the different treatments was calculated by using factors of 25 for CH4 and 298 for N2 O (298) (Forster et al., 2007). The global warming mitigation potential (GWMP) in the biochar/corn stalk treatments was calculated as follows: ( ) GWP- SOCBeq -SOCCeq GWMP = , (3) OC where GWP is the GWP of non-CO2 greenhouse gases in the biochar/corn stalk treatments, SOCBeq is the SOC (CO2 equivalents) © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 332 X. W. Lin et al. in the biochar/corn stalk treatments, SOCCeq is the SOC (CO2 equivalents: CO2 –eq.) in the control, and OC is the organic C input in the biochar/corn stalk treatments. Table 2 Above-ground biomass and yield compositions of wheat and soya bean Crop Biomass and yield compositions Treatment Mean P value Soya Biomass per plant / g 0.089 Data analysis General linear model–repeated measures define factors (SPSS 13.0, SPSS Inc., Chicago, IL, USA) were used to assess the significance of the effects of treatment, sampling day and their interactions on GHG emissions, wherein sampling day was treated as a within-subject variable and treatment was treated as a between-subject variable. For each measurement of GHG fluxes and the cumulative GHG emission, the significant difference among treatments was assessed using one-way anova and least significance difference (LSD). Pearson correlation coefficients between GHG fluxes and soil temperature and soil moisture were calculated. Differences in biomass and grain mass per plant between the biochar treatments and the control were compared with a t-test. All significant differences noted in the text are at the 0.05 level. Grain mass per plant / g Number of pods per plant Number of seeds per plant Hundred seed mass / g Wheat Biomass per plant / g Grain mass per plant / g Number of tillers per plant Number of seeds per plant Thousand grain mass / g Results Crop biomass and grain mass Biochar application (16 t ha−1 biochar) increased the above-ground biomass and grain mass per plant of soya bean by 11% (P = 0.089) and 24% (P = 0.057), respectively, when compared with the control (no biochar + crops) (Table 2). Biochar application increased the wheat above-ground biomass by 32% (P = 0.043) and its grain mass per plant by 28% (P = 0.040) when compared with the control treatment. The increase in grain mass per plant induced by biochar application resulted mainly from increased pod and grain numbers per plant for soya bean and thousand-grain mass for wheat. Soil organic carbon Biochar application at 16 and 32 t ha−1 significantly increased the SOC concentration (Table 3). Biochar application was linearly correlated with the SOC (r = 0.981, P < 0.001), increasing the SOC concentration by 31–298% compared with the control (P = 0.060, P < 0.001 and P < 0.001 for BC3.2, BC16 and BC32, respectively). Incorporating a large amount of corn stalk (7.8 t ha−1 ) into the soil did not increase the SOC significantly after 1 year. Biochar and corn stalk application increased the 𝛿 13 C value of the SOC significantly. The biochar contributed 18.5% of the SOC in the BC3.2 treatment, 53.9% of the SOC in the BC16 treatment and 72.3% of the SOC in the BC32 treatment, whereas the corn stalks contributed 7.3% of the SOC in the CS treatment. Most of the biochar C (82.3–99.4% in the biochar treatments) was sequestered in the saline soil, but only 16.8% of the corn stalk C was sequestered as SOC. Furthermore, 1 year of biochar and corn stalk application did not significantly change the C3 -SOC concentrations. BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control 15.7 ± 0.4 14.1 ± 0.6 6.4 ± 0.4 5.2 ± 0.2 24.5 ± 2.5 17.5 ± 1.8 33.7 ± 1.7 27.0 ± 1.5 19.0 ± 0.1 19.1 ± 0.1 6.3 ± 0.5 4.7 ± 0.2 2.9 ± 0.2 2.2 ± 0.1 2.5 ± 0.3 2.1 ± 0.1 58.5 ± 4.7 49.2 ± 2.2 49.0 ± 1.3 45.5 ± 0.3 0.057 0.085 0.042 0.888 0.043 0.040 0.277 0.151 0.061 BC16, 16 t ha−1 biochar application; Control, no biochar application; P value, the significant levels of the t-test. Carbon dioxide The soil CO2 emissions varied significantly with the season, with the mean daily CO2 emission rate varying from 52 mg m−2 hour−1 at the end of January to 781 mg m−2 hour−1 in the middle of August (Figure 1). Soil CO2 emission rates were affected significantly by the interaction between the treatment and the sampling day (Table 4). For example, the BC3.2, BC32 and CS treatments increased the soil CO2 emissions on two to eight occasions during the whole investigation period. However, the BC3.2, BC16 and BC32 treatments decreased the soil CO2 emissions significantly on one or two occasions. The cumulative CO2 emissions were greatest in the CS treatment during soya bean (36% more than the control) and wheat (14.1% more than the control) production and CO2 emissions in CS exceeded that of the control by 6.7 t CO2 ha−1 over two production cycles (Figure 2; Table 5). Biochar application had no significant impact on the cumulative CO2 emissions during soya bean growth, wheat growth and the whole investigation period. Methane and nitrous oxide The coastal saline soil was a weak source of CH4 in all treatments, with the daily mean CH4 flux varying from −35 to 350 μg m−2 hour−1 (Figure 3). The biochar and corn stalk applications did not influence the CH4 fluxes significantly during most of the sampling days. Corn stalk application increased the cumulative CH4 emissions by 30.0% more than the control during the whole investigation period, but the increase was not significant (Figure 4). © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 Biochar’s effects on GHGs, soil C cycle and crop growth 333 Table 3 Total soil organic carbon (SOC), the amount of biochar C and C3 SOC in the biochar or corn stalk treatments and summary of the analyses of variance Treatment BC3.2 BC16 BC32 CS Control anova Degrees of freedom Sum of squares Mean squares F value P value Total SOC / g kg−1 𝛿 13 C value / ‰ C4 in SOC / % C3 in SOC / g kg−1 C4 sequestration rate / % 4.5 ± 0.1 8.9 ± 0.3 13.8 ± 0.7 3.8 ± 0.3 3.5 ± 0.1 −20.93 ± 0.23 −17.52 ± 0.08 −15.75 ± 0.20 −21.94 ± 0.15 −22.72 ± 0.21 18.5 ± 2.5 53.9 ± 0.8 72.3 ± 2.2 7.3 ± 1.4 – 3.7 ± 0.2 4.1 ± 0.2 3.8 ± 0.1 3.5 ± 0.3 3.5 ± 0.1 82.3 ± 9.2 95.2 ± 2.0 99.4 ± 7.7 16.8 ± 2.1 – 4 237.53 59.38 157.85 < 0.001 4 107.92 26.98 214.25 < 0.001 3 8253.99 2751.33 274.90 < 0.001 4 0.81 0.20 1.20 0.369 3 13329.12 4443.04 39.27 < 0.001 BC3.2, BC16, BC32, CS and Control refer to 3.2, 16, 32 t ha−1 biochar application, 7.8 t ha−1 corn stalk application and the control, respectively. Figure 1 Effects of biochar and corn stalk application on soil CO2 fluxes. BC3.2, 3.2 t ha−1 biochar; BC16, 16 t ha−1 biochar; BC32, 32 t ha−1 biochar; CS, 7.8 t ha−1 corn stalk; Control, control treatment (microcosms without crop). Each bar represents LSD (least significant difference) at 5%. Figure 2 Effects of biochar and corn stalk application on the cumulative soil CO2 emissions. Vertical bars are standard errors. Table 5 Summary of the analyses of variance of the cumulative soil CO2 , CH4 and N2 O emissions from one-way anova Table 4 Summary of the analysis of variance of CO2 , CH4 and N2 O fluxes from repeated-measure anova Model Degrees of Sum of freedom squares CO2 Treatment 4 Date 34 Date × treatment 136 4 CH4 Treatment Date 34 Date × treatment 136 4 N2 O Treatment Date 34 Date × treatment 136 Mean square F value P value 293848.6 73462.2 6.04 0.010 16690288.8 490890.8 66.46 < 0.001 2301414.8 16922.2 2.29 < 0.001 74711.0 18677.8 0.61 0.667 4676952.7 137557.4 9.59 0.000 1393137.8 10243.7 0.71 0.988 14658.2 3664.5 3.86 0.038 691989.7 20352.6 14.81 < 0.001 230956.0 1698.2 1.24 0.065 The cumulative CH4 emissions did not differ significantly between the biochar treatments and the control during soya bean growth, wheat growth and across the two growth seasons. Large temporal variations in soil N2 O emissions were observed in all treatments and the mean daily N2 O emission rates ranged from 15 to 200 μg m−2 hour−1 (Figure 5). Two N2 O emission pulses were Period CO2 In soya bean season In wheat season Across two seasons CH4 In soya bean season In wheat season Across two seasons N2 O In soya bean season In wheat season Across two seasons Degrees of Sum of Mean F P freedom squares square value value 4 4 4 4 4 4 4 4 4 75.63 5.95 109.63 3.71 29.05 27.72 1.33 0.94 3.78 18.91 1.49 27.41 0.93 7.26 6.93 0.33 0.23 0.95 6.37 5.35 7.55 0.30 1.37 0.59 2.14 1.97 4.45 0.008 0.014 0.005 0.869 0.312 0.675 0.150 0.176 0.025 observed for all treatments after fertilizer application. The effects of biochar and corn stalk applications on N2 O emissions varied with the sampling day. For example, CS significantly increased the N2 O emissions more than the control or the biochar treatments on five occasions. The BC16 and BC32 treatments had significantly larger N2 O emissions than the Control or the BC3.2 treatments on one occasion, whereas the BC16 and BC32 treatments had significantly smaller N2 O emissions than the Control or the BC3.2 treatments on one to two occasions. Biochar application did not © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 334 X. W. Lin et al. Figure 6 Effects of biochar and corn stalk application on the cumulative soil N2 O emissions. Vertical bars are standard errors. Figure 3 Effects of biochar and corn stalk application on soil CH4 fluxes. Each bar represents LSD (least significant difference) at 5%. Table 6 Pearson correlation (r) coefficients between greenhouse gas (GHG) fluxes and soil temperature and moisture Treatment CO2 CH4 Figure 4 Effects of biochar and corn stalk application on the cumulative soil CH4 emissions. Vertical bars are standard errors. N2 O BC3.2 BC16 BC32 CS Control BC3.2 BC16 BC32 CS Control BC3.2 BC16 BC32 CS Control Soil moisture Soil temperature r r −0.260 −0.175 −0.095 −0.097 −0.031 −0.306 −0.280 −0.253 −0.273 −0.312 0.067 0.174 0.120 0.177 0.033 P value 0.009 0.083 0.349 0.422 0.760 0.002 < 0.001 0.020 0.006 0.002 0.508 0.085 0.235 0.080 0.748 0.664 0.659 0.688 0.658 0.673 0.128 0.102 0.112 −0.012 0.130 0.220 0.244 0.192 0.147 0.253 P value < < < < < 0.001 0.001 0.001 0.001 0.001 0.194 0.300 0.083 0.900 0.186 0.024 0.012 0.050 0.134 0.009 P value, the significant levels of Pearson correlation coefficients. Figure 5 Effects of biochar and corn stalk application on soil N2 O fluxes. Each bar represents LSD (least significant difference) at 5%. significantly affect the cumulative N2 O emissions (Figure 6). The cumulative N2 O emissions were greatest under the CS treatment, increasing the N2 O emissions by 20.9% more than the control during soya bean growth and by 13.6% during wheat growth, but the increases were not significant. The corn stalk treatment emitted significantly more N2 O than the control (17.5%) throughout the entire sampling period. Relationships between GHG fluxes and soil temperature and moisture Soil CO2 fluxes were positively correlated with soil temperature (r = 0.658–0.688, P < 0.05) for all treatments, while only the soil CO2 fluxes in the BC3.2 treatment were weakly negatively correlated (r = −0.260, P < 0.05) with soil moisture (Table 6). A weak negative correlation between CH4 fluxes and soil moisture was observed for all treatments (r = −0.253 to −0.316, P < 0.05). There was a weak correlation between N2 O fluxes and soil temperature for most of the treatments (r = 0.220–0.253, P < 0.05), except for the CS treatment (r = 0.147, P > 0.05). Global warming mitigation potential of the treatments No significant difference was observed for CO2 equivalents (GWP) of non-CO2 greenhouse gases between the biochar treatments and the control in each season and across both growth seasons (Table 7). Corn stalk application significantly increased GWP by 19.2% more than the control. All biochar treatments had negative global warming mitigation potentials (GWMPs) (−3.84 to −3.17 t CO2 -eq. ha−1 t−1 C), with no significant differences between the different biochar treatments. However, the GWMP of the corn stalk treatment (−0.11 CO2 -eq ha−1 t−1 C) was significantly less than that of the biochar treatments. © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 Biochar’s effects on GHGs, soil C cycle and crop growth 335 Table 7 Global warming potential (GWP) (t CO2 -eq ha−1 ) of non-CO2 greenhouse gases (GHGs) and per area annual global warming mitigation potential (GWMP)a (t CO2 -eq. ha−1 t−1 C) and summary of the analyses of variance Treatment BC3.2 BC16 BC32 CS Control anova Degrees of freedom Sum of squares Mean squares F value P value a The GWP in the GWP in soya bean the wheat season season Total GWP GWMPa 0.83 ± 0.12 0.97 ± 0.02 0.82 ± 0.01 1.05 ± 0.08 0.89 ± 0.03 0.74 ± 0.03 0.72 ± 0.10 0.75 ± 0.05 1.00 ± 0.12 0.83 ± 0.08 1.57 ± 0.09 1.69 ± 0.11 1.58 ± 0.05 2.05 ± 0.12 1.72 ± 0.03 −3.17 ± 0.67 −3.84 ± 0.28 −3.74 ± 0.26 −0.11 ± 0.89 – 4 0.11 0.03 2.03 0.165 4 0.16 0.04 2.12 0.153 4 0.46 0.11 4.89 0.019 3 27.99 9.33 8.92 0.006 Table 8 Soil pH, soil salt concentration (‰) and soil exchangeable cations (K+ , Na+ , Ca2+ and Mg2+ ) (mg kg−1 soil) in the biochar-treated (16 t ha−1 ) and control microcosms with crops (Experiment I) in June 2011 Properties Treatment Mean P value pH Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 Control BC16 9.2 ± 0.09 9.2 ± 0.11 1.3 ± 0.04 1.3 ± 0.05 87 ± 5 121 ± 11 48 ± 5 49 ± 2 1113 ± 89 1137 ± 88 154 ± 10 169 ± 17 0.920 Salt concentration K+ Na+ Ca2+ Mg2+ 0.920 0.043 0.792 0.861 0.487 P value is the significant levels of the t-test. calculation of GWMP is shown in the Materials and methods. Discussion Above-ground biomass Biochar application affects crop growth depending on the type of biochar, the crop and the type of soil (Van Zwieten et al., 2010). In this study, applying biochar to the coastal saline soil significantly increased wheat yield and increased the soya bean yield (although not significantly, P = 0.057) during the first year. Some studies have shown that biochar application improves the pH of acidic soil and the exchangeable K+ , Ca2+ and Mg2+ (mostly coming from biochar), which stimulates crop growth (Major et al., 2010; Van Zwieten et al., 2010). Applying biochar (16 t ha−1 ) to the saline soil did not affect the soil pH, the exchangeable Na+ , Ca2+ and Mg2+ concentrations or the salt concentration, but it significantly increased the exchangeable K+ concentration by 44% by the end of the study (Table 8). Increasing the soil exchangeable K+ increases the K+ :Na+ ratio in plants, which improves their salt tolerance and subsequently increases plant growth (Bohra & Doerffling, 1993). Therefore, the larger wheat grain mass per plant could result from more soil-available K+ introduced to soil by biochar with large amounts of available K+ and enhancement of crop K+ uptake (Lehmann et al., 2003). Biochar also improves soil fertility by increasing cation exchange capacity, water-holding capacity, nutrient retention through cation adsorption, fertilizer-use efficiency and symbiotic microorganisms and earthworm habitats, which would improve plant growth (Van Zwieten et al., 2010; Knoblauch et al., 2011; Lehmann et al., 2011). Therefore, the other mechanisms behind the increase in crop growth induced by biochar application to the saline soil should be studied. Soil organic C and respiration Some studies have shown that only 2–21% of plant residue C enters the SOC pool annually through humification (Lal, 2004; Xie et al., 2010). In our study, approximately 17% of the corn stalk C was captured by soil when the corn stalk was directly returned to the saline soil in 1 year. However, when plant residues were transformed into biochar (41% C recovery rate) and applied to soils, approximately 63% of the plant C was captured. Therefore, converting plant biomass into biochar could increase the C sequestration in saline soil by about four-fold, as indicated by the investigation in the first year. Several studies have suggested that biochar stimulates the loss of the native SOC (Hamer et al., 2004; Luo et al., 2011). In this study, biochar application did not significantly affect the non-biochar SOC. As found by Zimmerman et al. (2011), biochar application facilitated soil respiration during the first several months in our study. The initial increase in CO2 emission caused by biochar application may be caused by both mineralization of labile-C in biochar and stimulation of microbial activity and thereby enhanced mineralization of the soil organic C (Jones et al., 2011; Zimmerman et al., 2011; Case et al., 2012; Troy et al., 2013). However, biochar application did not affect the non-biochar SOC in this study. Thus, we suggest that most of the extra CO2 from biochar application during the soya bean season probably came from the rapid use of a small labile component of biochar (Zimmerman et al., 2011). However, the proportion of labile-C in biochar is small (0.1–6%) and always decomposed quickly (Jones et al., 2011; Knoblauch et al., 2011; Troy et al., 2013). In our study, this increase in soil respiration only occurred during the first few months and ceased during the later part of the investigation, while biochar application did not increase the cumulative CO2 emissions across both seasons. Non-CO2 greenhouse gases Some studies have shown that biochar application decreases methane emissions in paddy and tropical soils (Spokas et al., 2009), whereas others have reported increased methane emissions (Knoblauch et al., 2011; Yu et al., 2013). Such conflicting results © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 336 X. W. Lin et al. may be explained by the variable responses of methanogenic activity and methanotrophic activity to biochar application (Spokas et al., 2010). There are also changes in microbial and faunal populations (Lehmann et al., 2011), which are probably driven by different changes in soil physicochemical characteristics and the microbiological circumstances when different physicochemical biochars are applied to different soils (Van Zwieten et al., 2009; Spokas et al., 2010). For example, the increase in CH4 emissions induced by biochar application could be explained by the increased activities of methanogens because biochar increased soil pH and by emission of the CH4 from biochar pore spaces formed during production (Spokas & Reicosky, 2009; Yu et al., 2013). However, the improvement of soil aeration and porosity caused by biochar amendment may also increase methanotrophic activity and thereby decrease CH4 emission (Troy et al., 2013). Our results showed that the CH4 emissions were weakly and negatively correlated with soil moisture, similar to results reported by Cheng et al. (2010). However, biochar application did not significantly affect soil moisture (data not shown), which is in agreement with the field study of Hardie et al. (2014). Therefore, results from our experiment do not provide evidence that soil moisture has a role in biochar’s impact on soil CH4 emissions. In this study, biochar addition could increase anaerobic conditions without having an impact on soil pH (Table 8), which would favour CH4 oxidation. However, biochar application to the saline soil did not affect CH4 emissions, which is similar to the results from other agricultural and forest nursery soils (Spokas & Reicosky, 2009; Troy et al., 2013). In this study, corn stalk application increased soil N2 O emissions, which may be associated with enhanced denitrification rates (Cheng et al., 2012). Some studies show that the application of biochar derived from high-N manure or biochar/high-N animal excreta combinations increases soil N2 O emissions (Spokas & Reicosky, 2009; Clough et al., 2010; Bruun et al., 2011). The stimulation mechanism of biochar could be attributed to disturbance of nitrification, increasing N availability, improvement in the aeration of soil and stimulation of N2 O-producing activity of microbes or nitrifiers (Clough et al., 2010; Case et al., 2012; Saarnio et al., 2013). Other studies show that biochar application reduces soil N2 O emissions (Clough et al., 2010; Case et al., 2012). The mechanisms of N2 O reduction in biochar-amended soils could be attributed to reduced N availability due to biochar’s adsorption of substrates such as ammonium and nitrate (Bruun et al., 2011; Case et al., 2012), changes in microbial community structure (Bruun et al., 2011), a decrease in soil redox potential (Case et al., 2012) or microbial inhibition by volatile organic compounds contained in biochar (Spokas et al., 2010). At present, the mechanisms of biochar’s effect on N2 O emissions are not yet fully understood. The different physicochemical characteristics of biochar, soil types, biochar application rates and agricultural management measures could explain the different responses of N2 O emissions observed in these studies. Although biochar application changed some soil physicochemical properties in this study, its application did not affect the N2 O emission, which is in agreement with other field studies (Saarnio et al., 2013). The largest biochar application rate was approximately 1.5% by mass of soil in this study, whereas other studies have shown that N2 O emissions are restricted when biochar is applied at larger rates (> 4%) (Yanai et al., 2007; Spokas et al., 2009). Therefore, whether or not biochar application at greater rates could depress N2 O production in saline soil and enhance the GWMP of biochar needs further study. Global warming mitigation potential Applying corn stalks to saline soil may increase the SOC with increasing soil N2 O emissions. Therefore, the GWMP of corn stalk application to saline soil is nearly zero because of the amount of C sequestration that is offset by its contribution to the GWP of non-CO2 GHG emissions. The GWMP of biochar application to saline soil is greater than corn stalk application because of the greater C sequestration, without increasing N2 O emissions. The GWMP of biochar application to saline soil in this study was approximately 28–34 times greater than the value of corn stalk application. Charring plant residues and applying biochar to the soil instead of incorporating untreated harvest residues in saline soil may be a powerful strategy for mitigating global warming. However, GHG emissions during biochar production should be considered when calculating the GWMP of biochar application in soils (Woolf et al., 2010). Biochar production would lead indirectly to CO2 -equivalent emissions because of power requirements (electricity from fossil fuel), although there would be some offset of equivalent CO2 emissions by recovering pyrolytic gases (H2 , CO, CH4 , C2 H6 and C2 H4 ) (Woolf et al., 2010). From some previous studies, the net CO2 -equivalent emissions during biochar production were estimated as 0.44 t CO2 - to 4.20 t CO2 -eq. t−1 biochar (unpublished data) but depended on pyrolysis methods. When net CO2 -equivalent emissions during biochar production are minimized (slow pyrolysis with less energy input), the annual GWMP including the biochar production and application to saline soil was estimated as −2.90 t CO2 -eq ha−1 t−1 C, which was still greater (26 times) than that of the corn stalk treatment. In a system that uses electric heating with greater energy input, the annual GWMP including the biochar production and application to saline soil was estimated as 2.50 t CO2 -eq. ha−1 t−1 C, which would be the net CO2 -equivalent emissions. Therefore, biochar application would have the greater potential for mitigating global warming in saline soils when using the efficient pyrolysis techniques (such as continuous slow pyrolysis) with synthetic gas recovery and minimal energy input during its production. Conclusions Agricultural saline topsoils inherently have small SOC contents because of decades of little incorporation of biomass residue into the soil. However, biochar application quickly increases the SOC of saline soil, depending on the biochar application rate. Biochar application potentially increases soil C respiration loss during the early stage of treatment, but no significant effect was observed thereafter. Overall, the early CO2 loss only represents a small fraction of the biochar C, indicating that most of the biochar carbon © 2015 British Society of Soil Science, European Journal of Soil Science, 66, 329–338 Biochar’s effects on GHGs, soil C cycle and crop growth 337 could be sequestered in saline soil. Biochar application to saline soil had positive impacts on crop growth with increasing above-ground C sequestration, which would lead to more C sequestration in soil when the increased biomass is converted to biochar. Biochar amendment in saline soil did not affect the CH4 and N2 O cumulative emission significantly. The GWMP of the biochar treatments was greater than that of the corn stalk treatment. Thus, amending soils with biochar pyrolyzed from plant residues could be used as a means to manage C sequestration and mitigate global warming without increasing N2 O production in saline soils. 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