摘要
在全球变化的背景下,土壤有机碳的固定是温室气体减排与农业可持续发展过程中主要发展的方向。农业土壤在人类活动的影响下,对土壤碳库储存、演变的影响以及在碳循环过程中的作用日益受到人们的关注。目前,我们对于农田土壤固碳与温室气体减排的自然潜力和主要途径并不清楚。相关的固碳机理也有待深入研究。水稻土是我国重要的土壤类型之一,也是具有我国特色的代表性土壤。我国南方以种植水稻为主,水稻土在我国南方的土壤中占有重要地位。而且,我国南方的水稻土固碳潜力大。相对于其他类型的土壤而言,我国南方有些水稻土pH偏酸性,有机碳的含量也较高。但是我们对在低pH条件下的水稻土有机碳的固定机制还不清楚。我们提出假设,我国南方水稻土有机碳的固定是在团聚体物理保护下的化学结合与转化和稳定的共同作用机制。因此,我们选取了三种具有代表性的南方水稻土,同时选取了一种来源于长江流域的湿地土壤与水稻土进行比较,进行添加玉米秸秆的培养30、90和180天的室内实验。并且综合13C稳定性同位素示踪技术与热解质谱等分析手段,研究不同发生起源的水稻土和湿地土壤有机碳固定过程中的相关的机理问题。为水稻土固碳机制的研究提供新的资料。主要研究结果如下：
1.土壤有机碳在水稻土全土和团聚体颗粒组中的固定
通过室内培养实验对太湖地区黄泥土(TP)、红泥砂田(RP)、紫泥田(PP)和湿地土壤(MS)添加玉米秸秆培养30、90和180天时,土壤有机碳含量的变化研究结果表明,在这四种土壤当中,土壤有机碳的固定在太湖地区黄泥土和红泥砂田中比在紫泥田和湿地土壤中多。土壤的C/N与增加的有机碳呈显著相关,土壤的C/N可能与土壤固碳容量有关。通过对土壤团聚体颗粒组有机碳含量的分析得知,增加的团聚体有机碳含量在大粒级团聚体颗粒组(2000-200μm和200-20μm)中较高。随着培养时间的延长,水稻土和湿地土壤在2000-200μm颗粒组中分布的有机碳逐渐减少,水稻土有机碳有从2000-200μm粒级向20-2μm粒级中分布的趋势。而湿地土壤有机碳的分布以2000-200μm粒级为主。
结合13C稳定性同位素示踪技术,我们对水稻土添加玉米秸秆培养180天时土壤中水稻土来源的有机碳和玉米秸秆来源有机碳的分布结果进行了研究。研究结果也表明,太湖地区黄泥土和红泥砂田中无论是玉米秸秆来源碳还是水稻土来源的有机碳含量都高于紫泥田和湿地土壤,说明太湖地区黄泥土和红泥砂田的固碳能力更强,在团聚体颗粒组中,玉米秸秆来源有机碳主要集中在大粒级的团聚体(2000-200gm)中。
2.游离氧化铁在水稻土和湿地土壤固碳过程中的作用
培养180天时,铁铝键结合态有机碳与游离氧化铁之间的显著正相关关系表明了游离氧化铁与土壤有机碳的固定密切相关。土壤有机质中铁铝键结合态有机碳和胡敏素占土壤有机碳总量的90%左右,是有机质的主要组分。随着培养时间的延长,铁铝键结合态有机碳的比例减少,胡敏素的比例增加。在添加玉米秸秆培养30天时,增加的土壤有机碳与铁铝键结合态有机碳呈显著正相关关系,而到了180天时,增加的土壤有机碳与胡敏素呈显著正相关关系,说明有机碳在土壤中从固定到稳定化,经历了一个转化过程。在团聚体颗粒组中,各个有机质组分的分配不同。在水稻土和湿地土壤中,新碳主要以铁铝键结合态有机碳和胡敏素的形式被固定在大粒级的团聚体(2000-200μm和200-20μm)中。
3.疏水性有机质在土壤固碳过程中的作用
培养后四种土壤的热解质谱分析结果表明,虽然土壤有机质中的疏水性有机质(木质素和脂类物质)和亲水性有机质(多糖)的含量都增加了,但是随着培养时间的延长疏水性有机质和亲水性有机质的含量都逐渐降低。疏水性有机质比亲水性有机质降低的慢,表现的更稳定。与添加玉米秸秆培养30天的处理相比,培养180天时其疏水性有机质的百分含量更高,更进一步说明了疏水性有机质是土壤中的稳定性组分。土壤的粘粒含量、pH和游离氧化铁的含量是影响疏水性有机质含量的因子。与紫泥田和湿地土壤相比,太湖地区黄泥土、尤其是在红泥砂田中含有更多的疏水性有机质。这可能是有机碳在红泥砂田中更稳定的一个重要原因。而且,不同类型水稻土的土壤团聚体固定疏水性有机质的含量不同。当新鲜有机物质进入到水稻土和湿地土壤中时,疏水性有机质主要集中在大粒级的团聚体(2000-200μm和200-20μm)中。随着培养时间的延长,水稻土中增加的疏水性有机质含量在2000-200μm的粒级减少了,分别在其它粒级有所增加。而湿地土壤中增加的木质素和脂类物质含量在2000-200μm、200-20μm和20-2μm这三个粒级都降低了。
4.土壤铁铝键结合态有机碳的红外光谱和13C核磁共振分析
傅里叶变换红外光谱的研究结果表明,铁铝键结合态有机碳中的疏水性官能团如苯酚基团具有结构上的稳定性,对水稻土有机碳的固定起重要作用。并且疏水性有机质对亲水性有机质的保护作用可能是亲水性有机质(蛋白质)保持稳定的一个原因。13C核磁共振研究结果表明了,培养结束时,与紫泥田相比,太湖地区黄泥土和红泥砂田中含有较多的烷基碳。太湖地区黄泥土和红泥砂田团聚体颗粒组中的铁铝键结合态有机碳在2000-200μm和20-2μm粒级中芳香碳的含量较高,而紫泥土在200-20μm和<2μm的粒级中芳香碳含量较高。联系到团聚体中增加的疏水性有机质的结果,有可能铁铝键结合态有机碳疏水性基团(芳香碳和烷基碳)的含量变化与土壤团聚体颗粒组有机碳的稳定性密切相关。
以上研究结果表明,作物源碳在土壤中的固定主要集中在大粒级的团聚体(2000-200μm)中。游离氧化铁与水稻土有机碳的固定密切相关。疏水性有机质在分子结构上的稳定性是土壤有机碳保持稳定的一个重要原因。由于在太湖地区黄泥土和红泥砂田中含有较丰富的游离氧化铁和较高含量的疏水性有机质(木质素和脂类物质),有机碳在这两种水稻土中更稳定。水稻土有机碳的固定是在土壤团聚体的物理保护下经化学结合和转化,并最终达到分子结构上稳定的共同作用。
Sequestration of soil organic carbon (SOC) is main developed object in the process of reducing the emission of green house gases (GHGs) and sustainable development under the global change situation. In addition, a lot of people pay attention to the effect of agricultural soils in carbon storage and development including the carbon cycle at the same time. It is not clear to the potential and way of carbon sequestration in agricultural soils and GHGs reducing till now. While, the mechanism of carbon sequestration is also need to be studied. Paddy soil is a typical and main soil type in China soils. The main plant in the south of China is rice. Thus, paddy soils play an important role in the south of China. Moreover, the potential of carbon sequestration in paddy soils is high. Generally speaking, the pH was acidic, and the amount of SOC was high in some paddy soils in the south of China. However, the mechanism of carbon sequestration in these paddy soils is not clear now. We hypothesis that the carbon sequestration in paddy soils is conducted by interacted with iron oxides and convert to a stable status, and stabilize on molecular structure under the physical protection of aggregates. Therefore, three typical paddy soils developed from different pedogenesis in the south of China were used in this study. Moreover, a marsh soil without cultivated and developed from Yangtze River valley was also used in order to compared to paddy soils. Laboratory incubation experiment with maize straw for30,90and180days was conducted in three paddy soils and a marsh soil.13C stable isotope trace technique and off-line in the presence of tetramethylammonium hydroxide (TMAH) and followed by gas chromatography mass spectrometry (Pyr-TMAH-GC-MS) were used in order to study the mechanism of carbon sequestration in paddy soils and a marsh soil. Then, some new material could be provided for studying the mechanism of carbon sequestration. The main conclusions were as follows:
1. Sequestration of SOC in whole soils and aggregates of paddy soils and marsh soil
The changes of amounts of SOC incubated with maize straw for30,90and180days was studied in paddy soil TP, developed from clayey lacustrine deposits in the Tai Lake plain, paddy soil RP, derived from red earth in the rolling red soil area, paddy soil PP, formed on Jurassic purple shale and sandstone and marsh soil MS, developed from Yangze River valley. The increase in SOC was higher in soil TP and soil RP than in soil PP and soil MS. While, the C/N ratio significantly correlated to the increased SOC. Maybe the C/N ratio related to the capacity of carbon sequestration in soils. Moreover, increase in SOC of particle size fractions was mainly in coarse fraction (2000-200μmn and200-20μm). The distribution of SOC in particle size fractions transferred from coarse fraction (2000-200μm) to fine fraction (20-2μm) in paddy soils with time, but SOC mainly distributed in coarse fractions (2000-200μm) of soil MS.
In addition, different sources of SOC, such as SOC derived from paddy soils and maize straw, were also studied by13C isotope trace. It showed that there were more maize straw organic carbon sequestrated in soil TP and soil RP than in soil PP and soil MS, and there were more SOC derived from paddy soil in soil TP and soil RP too. It showed that the capacity of carbon sequestration in soil TP and soil RP is higher than in soil PP and soil MS. The maize straw organic carbon was mainly sequestrated in coarse fraction (2000-200μm) in results of13C isotope trace.
2. Effect of free iron oxide (Fed) on carbon sequestration in paddy soils and marsh soil
A positive correlation between Fe/Al-OC and free iron oxide (Fed) showed that the free iron oxide related to carbon sequestration. Both the Fe/Al-OC and humin were the main fractions of soil organic matter (SOM). The sum of them was more than90%in SOM. However, the percentage of Fe/Al-OC was decreased, but it was increased in humin with time. A positive correlation between increased SOC and increased Fe/Al-OC was found in30days of incubation with maize straw, but a positive correlation between increased SOC and increased humin was found in180days of incubation with maize straw. It showed that the convert from Fe/Al-OC to humin existed in carbon sequestration and was the process of carbon sequestration and stability. The distribution of the fractions of SOM was different in particle size fractions. The maize straw organic carbon was mainly sequestrated as Fe/Al-OC and humin in coarse fractions (2000-200μm and200-20μm) of paddy soils and marsh soil.
3. Effect of hydrophobic organic matter on carbon sequestration
The results of Pyr-TMAH-GC-MS analysis showed that increase in hydrophobic organic matter (lignin and lipids) and hydrophilic organic matter (polysaccharides) was found in this study. Then, both of them decreased with time, but the decrease in hydrophobic organic matter was slower than in hydrophilic organic matter. While, hydrophobic materials (lignin and lipids) were more stable than hydrophilic material (polysaccharides). Compared to30days of incubation with maize straw, the percentage of hydrophobic organic matter was higher in180days of incubation. It also showed that the hydrophobic organic matter was more stable than hydrophilic organic matter. Clay content, pH and amounts of free iron oxide were the effect factors of the amounts of hydrophobic materials in this study. There were more hydrophobic materials in soil TP and soil RP than in soil PP and soil MS. Maybe it was a reason for the high stability of SOC in soil RP. Moreover, the sequestration of hydrophobic organic matter in particle size fractions of various types of paddy soils was different. Hydrophobic materials mainly accumulated in coarse fractions (2000-200μm和200-20μm) when new organic matters were input in paddy soils and marsh soil. Then the increased amounts of hydrophobic organic matter decreased in the fractions of2000-200μm but, trended towards accumulating in other fractions of paddy soils with time. In contrary, the amounts of hydrophobic organic matter decreased with time in particle size fractions of2000-200μm,200-20μm, and20-2μm.
4. Analysis of Fe/Al-OC by FTIR spectroscopy and13C CPMAS-NMR
Hydrophobic functional groups such as phenol groups were stable fractions of Fe/Al-OC analyzed by Fourier transfer infrared (FTIR) spectroscopy. It played a significant role in carbon sequestration of paddy soils and marsh soil. While, it may was an important reason for the stability of hydrophilic materials which was protected by hydrophobic materials. In addition, the Fe/Al-OC extracted from soil TP and soil RP contained more alkyl groups than in soil PP analyzed by13C CPMAS NMR in the end of incubation. The content of aromatic groups of Fe/Al-OC was high in2000-200μm and20-2μm fractions in soil TP and soil RP, but it was high were in200-20μm and<2μm fractions in soil PP. If we consider the increase in hydrophobic organic matter together, the changes of aromatic and alkyl groups of Fe/Al-OC may relate to the stability of SOC in particle size fractions.
In summary, crop derived organic carbon was mainly sequestrated in coarse aggregates (2000-200μm). The amounts of Fed related to the carbon sequestration in paddy soils. Maybe the SOC were more stable in soil TP and soil RP because of the more Fed and hydrophobic organic matter. Carbon sequestration of SOC in paddy soils was that SOC interacted to Fed and converted to a stable status, and was stabilized on molecular structure under the protection of aggregates at the same time.
引文
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