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土壤有机质(soil organic matter, SOM)是指存留于土壤中的动植物残体、微生物体、根系分泌物和一些高度稳定的腐殖质等多种有机组分。SOM可通过保持基本的营养成分和水分以及改变土壤中关键的物理、化学和生物过程等途径维持植物、动物和微生物的生命,并在不断变化的环境中维持土壤生态系统的稳定性[1-2]。SOM矿化可直接提供植物生长所需的氮、磷等营养元素;另一方面,SOM可为土壤中的固氮菌提供其固氮所需要的能量,间接影响植物生长所需元素的可利用性[3-4]。SOM可改变土壤的物理条件、缓冲能力和离子交换能力,SOM损失会使土壤出现硬化、紧实和结块等现象,进而影响土壤的通气性、持水量和渗透能力;土壤缓冲能力和交换能力会随着腐殖质的增加而逐渐增强,研究发现[5]:土壤20%~70%的交换能力都是由土壤中的胶状腐殖质维持的。此外,SOM作为异养微生物所需的能量或底物来源,直接影响土壤微生物的数量和活性[6-7]。因此,SOM在土壤的物理、化学和生物转化过程中扮演着重要的角色。土壤是陆地生态系统最大的碳库,土壤有机碳总量达1 550亿t,作为土壤有机碳的最大来源,SOM在恢复和建立碳平衡、土壤碳和氮元素循环、环境可持续性和气候条件等方面起着至关重要的作用[8-9]。SOM积累和流失的速度直接影响大气中二氧化碳浓度,进而影响全球气候变化。SOM中碳的积累和流失通常通过2种方法进行估算,一种是直接通过测定有机质含量的变化计算,另外一种是根据放射性碳测定的有机物年龄推断,但对SOM中碳的估算高度依赖观测时间的范围[10]。在数月到数年内,新鲜植物凋落物分解过程中的质量损失速率接近于凋落物添加到土壤中的速率,因此,凋落物分解是土壤碳损失的主要途径;而在数千年的时间尺度上,碳储量的变化不能被直接观测到,通常是通过计算基岩,相似成土因素(基岩物质、气候和植被)下的风化时间来估算,因此土壤碳的数量和年龄受与风化有关的矿物变化控制。据估算,在过去的12 000 a里,人类的土地利用导致全球表层2 m土层的土壤流失了133 Pg碳[10-12]。认识控制SOM中碳稳定和释放的机制,探明近几十年到几个世纪内土壤有机碳储量的变化,对于预测全球气候变化的影响和制定提高土壤碳固存的管理策略具有重要意义[11, 13]。
然而,长期以来,解析SOM的化学成分十分困难,因为SOM是复杂的混合物,并在土壤中经历了短至数天、长至数千年的转化,化学成分十分复杂[14]。根据对生物降解的敏感性,SOM可分为易降解成分和腐殖质成分。前者主要是指仍能够判定出其前体(多糖、蛋白质和脂质)化学特征的成分,可用水解、浸提的方法进行测定;后者则是指复杂的有机聚合体,主要包括多酚、蛋白质、活性酶、脂质、多聚糖等及其衍生物,具有呈黄色或黑色、高分子量和难以降解的特征,靠常规方法往往难以测定[15-16]。近年来,热裂解气质联用(pyrolysis-gas chromatography/mass spectrometry,Py-GC/MS)技术被广泛用来测定SOM的化学成分和化学组成[17-19]。Py-GC/MS技术通过高温将SOM中的大分子降解成小分子和片段,然后通过气相色谱进行分离,是一种快速、有效、易操作、易重现的技术。SOM的稳定性主要取决于输入物质的化学性质[20]和分解过程[21]以及环境条件[22],所有这些因素都会在SOM组成上留下化学指纹。Py-GC/MS技术通过对SOM化学成分的解析,可提供SOM的“指纹图谱”(fingerprint),实现对SOM的定性分析,同时,通过测定热裂解产生的各种化学分子的相对丰度,可实现对SOM化学成分的定量分析[22-24]。
关于SOM化学组成研究进展已有一些报道。LEINWEBER等[25]从有机质前体物质和组成以及特定有机成分的功能方面进行了论述。KÖGEL-KNABNER等[26]总结认为Py-GC/MS可以有效追踪SOM成分的来源。LÜTZOW等[27]对Py-GC/MS在SOM稳定性方面的应用进行了分析,指出微生物能够分解自然界中的所有有机质,并认为微生物优先分解SOM中的易降解物质和选择性保留难降解物质这一机制只有在特定的环境下才成立。MEHRABANIAN[28]对Py-GC/MS表征SOM的优点进行总结,同时更新了脂肪酸、碳水化合物、木质素、芳香烃和含氮化合物组成的数据。DERENNE等[29]较为完整地总结了Py-GC/MS、热解场电离质谱法、热裂解质谱技术在SOM研究中的应用进展,从不同热裂解技术的优缺点,热裂解对SOM产物的鉴定,在土壤生态过程中的应用和研究SOM化学组成对环境变化的响应等4个方面进行了总结。MA等[30]对Py-GC/MS在不同生态系统中的应用和SOM化学组成及其影响因素进行了总结。目前,Py-GC/MS除用于表征不同环境下SOM化学组成之外,还从分子层面对SOM影响土壤元素循环的内在机制方面进行了一些研究。本研究在对SOM的来源和组成以及Py-GC/MS技术综述的基础上,重点阐述基于Py-GC/MS技术研究SOM化学的进展,为深入研究SOM在生态系统过程的作用提供参考。
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