不同培肥土壤颗粒有机碳的13C核磁共振与红外光谱对比分析
曲晓晶1,2, 吴景贵1,*, 李明明3, 张乐乐2, 曹笠珈2
1. 吉林农业大学资源与环境学院, 吉林 长春 130118
2. 吉林市农业科学院, 吉林省 吉林市 132101
3. 双辽市环境监测站, 吉林 双辽 136400
摘要

为明确颗粒有机碳在土壤固碳中的作用机制, 对比研究了不同有机培肥土壤颗粒有机碳的结构差异。 以单施化肥处理为对照, 选择了四种有机物料进行定位培肥试验, 利用13C NMR和红外光谱技术对比分析不同有机培肥对土壤颗粒有机碳结构的影响。 结果表明: 颗粒有机碳以脂肪碳和含氧基团为主, 脂化度高于75%, 含氧官能团含量高于50%; 不同有机培肥对土壤颗粒有机碳结构的影响差异性显著, 树叶培肥在提高颗粒有机碳芳香度的同时, 亲水性也大幅度提高, 比单施化肥处理(对照)提高了0.78%; 短期内, 牛粪、 秸秆和树叶培肥均可提高土壤颗粒有机碳的芳香度, 但从长远角度分析, 牛粪和秸秆培肥更利于土壤颗粒有机碳的稳定, 尤其是秸秆培肥, 其颗粒有机碳的芳香度分别比对照和牛粪培肥高0.35%和0.11%, 而亲水性远低于二者; 红外光谱与核磁分析的结果基本一致, 红外光谱可用于大量样品的颗粒有机碳结构初步筛选。

关键词: 颗粒有机碳; 固体13C核磁共振; 红外光谱; 有机培肥
中图分类号:S153 文献标志码:A
Contrast Analysis of 13C Nuclear Magnetic Resonance and Infrared Spectroscopy of Particulate Organic Carbons in Different Fertilizations
QU Xiao-jing1,2, WU Jing-gui1,*, LI Ming-ming3, ZHANG Le-le2, CAO Li-jia2
1. College of Resources and Environmental Sciences, Jilin Agricultural University, Changchun 130118, China
2. Jilin City Academy of Agricultural Sciences, Jilin 132101, China
3. Shuangliao City Environmental Monitoring Station, Shuangliao 136400, China
*Corresponding author e-mail: wujingguiok@163.com
Abstract

This paper comparatively studied the structural differences of particulate organic carbon (POC) in different organic fertilizations, to clear the mechanism of action of POC in soil carbon sequestration. Compared with chemical fertilization as the control, four kinds of organic material for this positioning fertilizer experiment were chosen, and the effects we analyzed of different organic fertilization on the structure of POC through the13C Nuclear Magnetic Resonance (NMR) and Infrared Spectroscopy (IR). The results showed that POC was mainly composed of oxygen-containing groups and aliphatic structures, in which aliphaticity is higher than 75% and the content of oxygen-containing groups are higher than 50%; Different organic fertilization had greater difference impact on POC’s structure, and leaves fertilization could be improve POC aromaticity. At the same time, hydrophilic also increased significantly, about 0.78% than the control; Cow dung, maize straw or leaves could increase the aromaticity of POC in the short-term, the cow dung or straw treatment was more favorable for the stability of POC. Especially the straw treatment which aromaticity was higher 0.35% and 0.11% than control and cow dung, and the hydrophilicity was far lower than the two. The results of Infrared spectrum and nuclear magnetic analysis were basically identical, infrared spectrum can be used for preliminary screening for a large number of POC samples.

Keyword: Particulate organic carbon; 13C Nuclear magnetic resonance; Infrared spectrum; Organic fertilization

Introduction

Particulate organic carbon (POC) is an important part of soil active organic carbon, between fresh animal and plant residues and humification of organic matter, it was considered as temporary or transition organic carbon, POC’ s velocity of turnover in the soil is very fast, commonly 5~20 years[1, 2] , and it is also the sensitive index that judgment the external factor impact on soil organic carbon in short time[3, 4].

At present, there are many studies about POC, while the study of different organic fertilization on POC is less[5], and select different kinds of organic material for comparative study on POC is more less. The study has shown that POC has physics protective effect on soil aggregate, and conductive to soil carbon sequestration[6]. Through the mineralization cultivation experiment, Benbi found that the composition of soil particles easily decomposed and mineralization, not good for soil organic carbon accumulation[7]. As you see, there are some dispute over the function of POC on soil carbon sequestration. We must understand POC’ s structure conversion in farming, and then make clear its carbon sequestration operation mechanism. However, the study on structure of POC is less, and has not yet proved. So, by referring the study of ZhouPing in this paper[8], extracting POC from different fertilizer of soil, and applying solid-state 13C Nuclear Magnetic Resonance (NMR) and Infrared Spectroscopy(IR), this paper studied the POC’ s structure and the difference of compositon. It will provide theoretical basis at exploring the organic carbon operation mechanism in the process of carbon sequestration.

1 Experimental Design
1.1 Sample extraction

We collected samples from Lishu County Siping City Jilin Province, and conducted the positioning of the organic fertilizer experiment for three years. The soil was black , taken the topsoil (0~20 cm) for experimental analysis. There were 5 kinds of treatments in this experiment: applying chemical fertilizer(CK), cow dung combined with chemical fertilizer(A), hen dung combined with chemical fertilizer(B), corn stalk combined with chemical fertilizer(C) and leaves combined with chemical fertilizer(D). Among them, the content of chemical fertilizer was consistent, with other organic materials referred to the carbon contents. Each treatment repeated three times, with 15 plots in total. Five soil samples were collected in each plot, accorching to the “ S” sype sampling method, then mixed topether for are smaple.

The extraction method of POC was wet screening[8, 9]: weighed 30 g air-dried soil samples which be sieved in the diameter of 2 mm, then putted them into 250 mL triangular flask, with 200 mL 0.5 g· L-1 (NaPO3)6 added, and oscillated 16 hours. Soil suspension was sieved in the diameter of 0.053 mm. Repeated washing with distilled water, and soil granular component was left on the sieve, at 60 ℃ oven dried to constant weight. Then grinded and sieved in 0.149 mm for standby application.

1.2 Sample Characterization

Used American NICOLET infrared spectrometer to analysis the Infrared Spectroscopy, and scan mode was 4 000~400 cm-1. POC samples were grinded less than 2 μ m with agate mortar, mixed KBr in proportion of 1∶ 100, and then grinded together. Finally 0.5~2 mg composite samples, tabletted, and scanned.

For 13C nuclear magnetic resonance (NMR) analysis, used superconductivity nuclear magnetic resonance spectrum AVANCE 400 WB(EX18-0011)to measure. 13 C-cross-polarization magic Angle spinning technology, Spectral frequency was 75.5 MHz, the rotor diameter was 4 mm, and Rotating frequency was 14 kHz[8, 10], accumulated 16 000 times.

2 Results and Discussion
2.1 13C NMR Analysis

13C NMR spectrogram are shown in Fig.1, mainly attribution of chemical shift to see table 1. By the Fig.1 shows, POC is mainly composed of aliphatic and aromatic carbon. Especially the content of aliphatic carbon is more than 75%(Table 1). Similar to other scholars’ spectra[8]. The order of aromaticity is D> C> A> CK> B, aromaticity of D is significantly higher than other treatments, at least higher 3.5%. The aromaticity of B was slightly lower than CK; the difference was only 0.06%. The oxygen-containing functional groups of POC are more than 50%, declaring that POC has certain hydrophilicity and unstable structure. The order of oxygen-containing functional group is D> CK> A> C> B, and an average of more than 50%, D or CK has exceeded 60% (Table 1), which states that POC is mainly composed by oxygen aliphatic carbon, POC of D or CK has stronger hydrophilic. Because of cow dung, straw, and the leaves contain a certain amount of lignin, while chicken manure is mainly composed by carbonhydrate, protein, POC of C or D mainly comes from aliphatic higher plant source of stalks and leaves, POC of A comes from lignin of cow dung and microbial source aliphatic[11], but the chicken manure has no source of lignin, because POC aromaticity of B is lower than other organic treatments. So, although the chicken manure resulted in POC aromaticity decline, it improves its hydrophobicity; leaves or cow dung greatly improves aromaticity, but it also improved the hydrophilic POC; there are both higher aromaticity and certain hydrophobic in straw fertilizer soil’ s POC, that is all the organic material who improved the aromaticity of POC, the stalk’ s hydrophilic is the lowest (the content of oxygen containing functional groups was 54.36%). It illustrated that in a short term, cow dung, straw or leaves can improve the stability of the POC, but for this short term conclusion needs to be further studied to confirm. From a long-term perspective, only straw fertilizer can guarantee the stability of POC, and a large number of studies have confirmed the stalk’ s function of carbon sequestration.

Fig.1 Cross polarization magic angle spinning 13C-NMR spectra of particulate organic carbon (POC) [A, B, C, D and CK] isolated from the soil

Table 1 Functional groups from the 13C NMR spectra
2.2 Infrared Spectroscopic Analysis[12]

As shown in Fig.2, the main absorption peak of sample’ s IR is caused by methyl C— H (2 920 cm-1), methylene C— H (2 860 cm -1), aromatic groups C=C (1 620 cm-1) and C— O (1 030 cm-1) stretching vibration. The aromatic carbon’ s intensity of absorption bands at 1 620 cm-1 is lower, significantly less than 1 030 cm-1, that is POC has lower aromaticity and higher aliphaticity. The analysis results are consistent with the Nuclear Magnetic (Fig.1). The absorption band of 1 030 cm-1 is caused by primary alcohol, ether, ester and carboxyl of C— O stretching vibration. The analysis results are consistent with the 13CNMR(Fig.1). Aromatic group absorption band of 1 620 cm-1’ s intensity is A, C and CK obviously stronger than B, close to the Nuclear Magnetic results, while aliphatic carbon absosption band of 2 920 cm-1 shows that B and C is stronger than other treatments, and it illustrated that B and C has higher content of aliphatic carbon, Same as the result of the 13C NMR (Table 1).

Fig.2 Infrared spectra (IR) of POC isolated from the soil

3 Conclusion

(1) (1)POC is mainly composed by aliphatic carbon and oxygen-containing group. The impact of organic fertilizer on POC structure’ s difference is remarkable, also has obvious influence on its aromaticity and molecular polarity, In the short term, the cow dung, stalk, and the leaves are raised the aromaticity of POC, conducive to the stability, but effect of Chicken manure is not obvious, However, in the long term, the cow dung and stalk are conducive to the stability of the POCEspecially the stalkand leaves improve the aromaticity of POC, at the same time, with hydrophilic rising sharply, chicken manure opposite. Therefore, long--term effect of leaves, and chicken manure fertilizing remains to be further researched.

(2) (2)The results of Infrared Spectroscopic Analysis and Nuclear Magnetic have higher consistency. It is thus clear that Infrared Spectroscopic can reflect POC’ s structural characters in a certain extent, compared with Nuclear Magnetic. Infrared Spectroscopic cost is low and testing speed is fast, which can be used in the study of POC structure tentative exploration in the future or a large number of samples’ optimized selection.

The authors have declared that no competing interests exist.

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