广西红树林表层沉积物中活性铁氧化物对有机碳的保存

相志远; 张芬芬; 魏金娥; 杜金洲

doi:10.12284/hyxb2024114

广西红树林表层沉积物中活性铁氧化物对有机碳的保存

doi: 10.12284/hyxb2024114

华东师范大学河口海岸学国家重点实验室，上海 200241

基金项目: 国家重点研发计划项目“气候变化和人类活动对海上丝路沿线国家滨海蓝碳生态系统的耦合影响机制与合作研究”（2022YFE0209300）；国家自然科学基金面上项目“北部湾典型砂质海岸海底地下水溶解有机碳结构组成及其入海通量研究”（No. 41373119）。

详细信息

作者简介:
相志远（1999—），男，安徽省滁州市人，研究方向为铁−碳耦合生物地球化学循环。E-mail：xzy19990722@sina.com

通讯作者:
张芬芬，研究员，博士生导师，研究方向为碳的生物地球化学循环、环境记录与全球变化。E-mail：ffzhang@sklec.ecnu.edu.cn

中图分类号: P736.4
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出版历程
- 收稿日期: 2024-02-27
- 修回日期: 2024-06-06
- 网络出版日期: 2024-08-19
- 刊出日期: 2024-11-01

The preservation of organic carbon by active iron oxides in surface sediments from Guangxi mangroves

State Key Laboratory of Estuarine and Coastal Research, East China Normal University, Shanghai 200241, China

摘要

摘要: 铁氧化物在全球土壤（沉积物）有机碳（Organic Carbon，OC）存储中具有重要作用。红树林湿地同时具有陆源与海源输入，为活性铁氧化物（Fe_R）对OC的保存提供了独特的生境。然而红树林表层沉积物中Fe_R对OC保存过程中的影响因素以及Fe_R对OC组分的选择性尚不明确。本研究选择广西大风江入海口和茅尾海周围受到潮汐与河流影响的天然红树林生境中的表层沉积物，研究沉积物中铁结合有机碳（Fe-OC）含量以及组分的变化。结果表明，大风江入海口与茅尾海表层沉积物中Fe-OC平均含量分别为0.16% ± 0.07%与0.17% ± 0.07%，在总有机碳（TOC）中所占比例（f_Fe-OC）分别为16.2% ± 5.04%与10.9% ± 5.63%，主要保存方式为吸附。Fe_R对OC的保存受到沉积物粒度、Fe_R含量与形态以及TOC来源与组分的影响。TOC、Fe_R与Fe-OC主要分布在粒度较小的沉积物组分中。表层沉积物中铁的存在形式以Fe³⁺为主，占总铁的87.42%，在高盐度沉积物中相对更高。Fe_R会选择性保存结合δ¹³C值（稳定性碳同位素自然丰度）偏正的OC与芳香族OC。与茅尾海相比较，大风江入海口表层沉积物Fe-OC中类蛋白荧光组分占总荧光组分的比例更高。类蛋白荧光组分占比随Fe-OC∶Fe摩尔比升高而升高。本研究有助于明确广西红树林表层沉积物中Fe_R对OC的选择性保存机制，加深对陆海界面沉积物中OC的保存过程的了解。
- 红树林 /
- 沉积物 /
- 铁结合有机碳 /
- 稳定性碳同位素
Abstract: Iron oxides play a significant role in the global soil (sediment) organic carbon (OC) storage. Mangrove wetlands, receiving both terrestrial and marine inputs, provide a unique habitat for the preservation of organic carbon by reactive iron oxides (Fe_R). However, the impact of Fe_R in the surface sediments of mangroves on the preservation process of OC, as well as the selectivity of Fe_R towards different OC components, is still unclear. The surface sediments in the present work was collected in the natural mangrove areas around the estuaries of the Dafeng River and Maowei Sea in Guangxi, which are highly influenced by tides and rivers. The research was focused on the changes in the content and composition of iron-bound organic carbon (Fe-OC) in sediments. The results indicated that the average content of Fe-OC in surface sediments in the estuaries of Dafeng River and Maowei Sea was 0.16% ± 0.07% and 0.17% ± 0.07%, respectively. These values represented 16.2 ± 5.04% and 10.9 ± 5.63% of the total organic carbon (TOC) content in the respective sediments, which were primarily preserved through adsorption. Furthermore, the preservation of OC by Fe_R was influenced by the sediment particle size, the content and form of Fe_R, and the source and composition of TOC. TOC, Fe_R and Fe-OC were mainly distributed in the smaller grain size sediment fractions. The predominant form of iron in surface sediments was Fe³⁺, accounting for 87.42% of the total iron, and was relatively higher in high salinity sediments. Fe_R selectively preserved OC with higher δ¹³C (stable carbon isotope natural abundance) and aromatic OC. Compared with the Maowei Sea, the proportion of protein-like fluorescent components in Fe-OC of surface sediments from the Dafeng River estuary was higher and the proportion of protein-like fluorescent components increased as the molar ratio of Fe-OC∶Fe increased. This study helps to clarify the selective preservation mechanism of OC by Fe_R in mangrove surface sediments in Guangxi, and deepen our understanding of the preservation process of OC in land-sea interface sediments.
- mangroves /
- sediments /
- iron-bound organic carbon /
- stable carbon isotope

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图 1 采样站位

a. 广西壮族自治区钦州市钦南区海域，b. 茅尾海（MW），c. 大风江入海口（DF）

Fig. 1 Sampling site

a. Marine area of Qinnan District, Qinzhou in Guangxi; b. Maowei Sea (MW); c. the estuary of Dafeng River (DF)

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图 2 广西大风江（DF）与茅尾海（MW）红树林表层沉积物中TOC含量（a）、Fe_R含量（b）、黏土与粉砂比例（c）、Fe-OC含量（d）与f_Fe-OC（e）

Fig. 2 The contents of total OC (a), Fe_R (b), the proportion of clay + silt (c), Fe-OC (d) and f_Fe-OC (e) in surface sediments in the estuary of Dafeng River (DF) and Maowei Sea (MW) from Guangxi mangroves

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图 3 广西大风江（DF）与茅尾海（MW）红树林表层沉积物中原始样品与DCB处理后样品的δ¹³C值分布

Fig. 3 Distribution of δ¹³C in surface sediments of original samples and after DCB treatment samples in the estuary of Dafeng River (DF) and Maowei Sea (MW) from Guangxi mangroves

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图 4 广西大风江入海口（DF）与茅尾海（MW）红树林典型表层沉积物的穆斯堡尔谱图

a. DF-1-A站位，b. DF-6-A站位，c. MW-3-A站位。D1：顺磁性高自旋亚铁的双峰（para-Fe²⁺）；D2：低自旋三价铁的双峰（para-Fe³⁺）

Fig. 4 Mössbauer spectra of typical surface sediments in the estuary of Dafeng River (DF) and Maowei Sea (MW) from Guangxi mangroves

a. DF-1-A site, b. DF-6-A site, c. MW-3-A site. D1: doublet for paramagnetic high-spin ferrous iron (para-Fe²⁺); D2: doublet for low-spin ferric iron (para-Fe³⁺)

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图 5 广西大风江入海口（DF）与茅尾海（MW）红树林表层沉积物在DCB处理前后1800～1400 cm⁻¹范围内衰减全反射−傅里叶变换红外光谱差异（ATR-FTIR）

红线为原始样品，黑线为DCB处理后样品。所有光谱均经过背景校准

Fig. 5 Variations in attenuated total reflectance-Fouriertransform infrared (ATR-FTIR) spectra in the 1800−1400 cm⁻¹ range for surface sediments in the estuary of Dafeng River (DF) and Maowei Sea (MW) from Guangxi mangroves before and after DCB treatment

The red line represents the original sample, while the black line represents the sample after DCB treatment. All spectra are background-corrected

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图 6 广西大风江入海口（DF）与茅尾海（MW）红树林表层沉积物在DCB处理前后3000～2800 cm⁻¹范围内衰减全反射−傅里叶变换红外光谱差异（ATR-FTIR）

红线为原始样品，黑线为DCB处理后样品。所有光谱均经过背景校准

Fig. 6 Variations in attenuated total reflectance-Fouriertransform infrared (ATR-FTIR) spectra in the 3000−2800 cm⁻¹ range for surface sediments in the estuary of Dafeng River (DF) and Maowei Sea (MW) from Guangxi mangroves before and after DCB treatment

The red line represents the original sample, while the black line represents the sample after DCB treatment. All spectra are background-corrected

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图 7 广西大风江入海口（DF）与茅尾海（MW）红树林表层沉积物原始样品与DCB处理后含氮化合物（a）、脂肪族（b）、芳香族（c）在总结构基团中相对比例与平均值百分比差异（d）

Fig. 7 Relative proportions of nitrogenous compounds (a), aliphatics (b), aromatics (c) in the total structural groups, and the average percentage difference (d) in surface sediment original samples and after DCB treatment in the estuary of Dafeng River (DF) and Maowei Sea (MW) from Guangxi mangroves

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图 11 广西大风江与茅尾海红树林表层沉积物 C/N摩尔比与δ¹³C值相关关系（a）与C/N摩尔比与δ¹³C值分布（b）（改自文献[48]）

Fig. 11 The correlation between C/N molar ratio and δ¹³C values(a) , and the distribution of C/N molar ratio and δ¹³Cvalues(b) in surface sediments in the estuary of Dafeng River and Maowei Sea from Guangxi mangroves [48]

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图 8 广西红树林表层沉积物的三角图分布

a. 大风江入海口，b. 茅尾海

Fig. 8 Triangular distribution of surface sediments from Guangxi mangroves

a. The estuary of Dafeng River, b. Maowei Sea

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图 9 广西红树林表层沉积物各参数相关性

a. 大风江入海口，b. 茅尾海。椭圆形部分为皮尔逊相关性表示图，红色为正相关，蓝色为负相关，星号表示相关性显著（p < 0.05）；数字部分为具体的皮尔逊相关性系数大小

Fig. 9 Correlation analysis of various parameters in surface sediments from Guangxi mangroves

a. The estuary of Dafeng River, b. Maowei Sea. The elliptical part represents Pearson correlation representation, where red indicates positive correlation, blue indicates negative correlation, and asterisks denote significant correlations (p < 0.05); the number part represents specific Pearson correlation coefficients

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图 10 广西大风江入海口与茅尾海红树林表层沉积物中黏土、粉砂占比与TOC（a）、Fe_R（b）、Fe-OC（c）含量的相关关系

阴影部分为95%置信带

Fig. 10 The correlation between the proportions of clay and silt and the contents of TOC (a), Fe_R (b) and Fe-OC (c) insurface sediments in the estuary of Dafeng River and Maowei Sea from Guangxi mangroves

The shaded part is 95% confidence band

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图 12 广西红树林表层沉积物中Fe-OC的荧光组分与Fe-OC∶Fe摩尔比的相关关系

a. 大风江入海口， b. 茅尾海。阴影部分为95%置信带

Fig. 12 The correlation between the fluorescent components of Fe-OC and the Fe-OC∶Fe molar ratio in surface sediments from Guangxi mangroves

a. The estuary of Dafeng River, b. Maowei Sea. The shaded part is 95% confidence band

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A1 茅尾海与大风江入海口表层沉积物穆斯堡尔谱

A1 Mössbauer spectra of surface sediments in the Maowei Sea and the Dafeng River estuary

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A2 广西红树林表层沉积物在DCB处理前后3500～500 cm⁻¹范围内衰减全反射−傅里叶变换红外光谱差异（ATR-FTIR）

红线为原始样品，黑线为DCB处理后样品。所有光谱均经过背景校准

A2 Variations in attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra in the 3500～500 cm⁻¹ range for surface sediments from Guangxi mangroves, before and after DCB treatment.

The red line represents the original sample, while the black line represents the sample after DCB treatment. All spectra are background-corrected

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A3 大风江入海口（a）与茅尾海（b）表层沉积物中Fe-OC的荧光组分差异

A3 Differences in the fluorescence composition of Fe-OC in the surface sediments in the estuary of Dafeng River (a) and Maowei Sea (b)

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表 1 广西大风江入海口与茅尾海红树林表层沉积物中Fe-OC荧光组分的鉴定

Tab. 1 Identification of fluorescent components of Fe-OC in surface sediments in the estuary of Dafeng River and Maowei Sea from Guangxi mangroves

组分	Ex. Max./nm	Em. Max./nm	荧光组分
C1	240	426	类似于陆源微生物类腐殖质^[30]
C2	295	498	类似于陆源腐殖质^[31−32]
C3	220和280	302	类似于海源酪氨酸样和蛋白质样^[33]
C4	270	486	类似于陆源类腐殖质^[34]

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表 2 全球典型湿地类型铁氧化物与有机碳结合情况（改自文献[44]）

Tab. 2 The combination of iron oxides with organic carbon in global typical wetland types [44]

站位	站位类型	pH值	占比/%	Fe³⁺/(μmol·g⁻¹)	SOC/(mg·g⁻¹)	Fe-bound C/(mg·g⁻¹)	f_OC-Fe/%	Fe-OC∶Fe摩尔比	参考文献
全球海洋	河口/海洋沉积物	–	–	–	–	–	21.5 ± 8.6	4.0 ± 2.8	Lalonde等^[7]
沃斯托克湖，美国	河流沉积物（新生）	–	–	47.0 ± 23.1	6.2 ± 1.1	0.7 ± 0.6	8.1 ± 3.2	0.5 ± 0.2	Shields等^[11]
沃斯托克湖，美国	河流沉积物（成熟）	–	–	83.5 ± 15.9	31.5 ± 5.2	7.1 ± 5.2	20.2 ± 3.8	5.0 ± 1.7	Shields等^[11]
沃斯托克湖，美国	河流沉积物（老化）	–	–	97.6 ± 12.4	42.2 ± 18.5	8.5 ± 1.3	15.0 ± 4.3	4.9 ± 2.7	Shields等^[11]
东英吉利亚，英国	泥碳地	6.2 ± 0.1	–	–	–	–	10.3 ± 2.2	–	Wen等^[45]
苏比克，菲律宾	红树林湿地	–	–	–	11.0 ± 4.0	1.7 ± 0.6	15.0 ± 9.0	0.8 ± 0.5	Dicen等^[4]
奥布布，菲律宾	红树林湿地	–	–	–	12.0 ± 2.0	1.4 ± 0.2	12.0 ± 2.0	14.6 ± 3.5	Dicen等^[4]
渤海，中国	海岸沉积物	–	17.9 ± 5.4	44.5 ± 10.4	6.2 ± 2.0	0.8 ± 0.7	11.5 ± 8.3	1.6 ± 1.4	Wang等^[35]
南黄海，中国	海岸沉积物	–	15.7 ± 7.2	38.0 ± 4.6	7.5 ± 3.5	0.8 ± 0.8	8.8 ± 7.7	1.7 ± 1.8	Ma等^[36]
东海，中国	海岸沉积物	–	18.6 ± 7.1	41.9 ± 14.9	5.5 ± 2.0	0.7 ± 0.5	13.2 ± 8.9	1.5 ± 1.3	Ma等^[36]
长江口，中国	海岸沉积物	–	24.3 ± 7.4	157.3 ± 39.3	5.4 ± 2.3	–	6.1 ± 2.1	0.2 ± 0.1	Zhao等^[10]
长江口，中国	海洋沉积物	–	25.7 ± 17.1	54.6 ± 9.0	3.2 ± 1.6	–	9.4 ± 5.1	0.4 ± 0.3	Zhao等^[10]
长江口，中国	河口沉积物	–	7.8 ± 7.2	102.9 ± 14.3	3.2 ± 2.2	–	11.3 ± 3.6	0.3 ± 0.2	Zhao等^[10]
神农架，中国	泥碳地	5.1 ± 0.2	–	100.0 ± 96.4	161.1 ± 73.3	–	12.8 ± 4.6	–	Zhao等^[46]
三江平原，中国	平原湿地（植被区）	6.5 ± 0.3	–	80.4 ± 1.8	44.2 ± 5.5	7.8 ± 0.3	17.8 ± 1.3	–	Duan等^[47]
三江平原，中国	平原湿地（光滩）	6.8 ± 0.2	–	53.6 ± 21.4	41.6 ± 2.9	2.1 ± 1.1	5.7 ± 2.7	–	Duan等^[47]
青藏高原，中国	高寒湿地	7.4 ± 0.4	–	30.4 ± 14.3	140.0 ± 15.0	–	8.6 ± 3.2	–	Wang等^[35]
闽江口，中国	潮间湿地	7.1 ± 0.2	13.5 ± 5.5	105.4 ± 21.4	12.8 ± 2.7	3.0 ± 0.6	24.5 ± 6.0	11.0 ± 4.5	Bai等^[44]
茅尾海，中国	红树林湿地	4.8 ± 0.9	17.4 ± 4.6	–	19.2 ± 1.2	1.7 ± 0.7	10.9 ± 5.6	0.7 ± 0.3	本研究
大风江入海口，中国	红树林湿地	6.7 ± 0.9	21.4 ± 7.5	–	10.2 ± 0.5	1.6 ± 0.7	16.2 ± 5.0	0.6 ± 0.3	本研究
注：“−”表示无数据。

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A1 大风江入海口红树林表层沉积物主要理化参数

A1 Main physicochemical parameters of the surface sediments in the mangrove in the estuary of Dafeng River

样品编号	pH值	电导率/(mS·cm⁻¹)	盐度	TN含量/%	TOC含量/%	黏土占比/%	粉砂占比/%	砂占比/%	C/N摩尔比
DF-1-A	6.18	8.44	6.90	0.14	1.55	27.68	48.79	23.55	12.9
DF-2-A	8.18	2.95	14.3	0.08	0.77	18.98	33.80	47.23	11.2
DF-3-A	6.64	4.47	4.37	0.08	0.90	17.49	27.63	54.89	13.1
DF-3-B	5.73	3.55	17.1	0.12	1.59	18.93	32.97	48.11	15.5
DF-3-C	6.37	3.57	19.3	0.08	1.14	13.62	25.08	61.31	16.6
DF-4-A	6.59	4.51	14.7	0.07	0.61	19.92	30.25	49.85	10.2
DF-4-B	6.38	3.60	21.3	0.05	0.53	10.11	18.52	71.37	12.4
DF-4-C	6.97	4.41	23.4	0.08	0.89	20.94	35.67	40.84	13.0
DF-5-A	5.92	7.02	3.08	0.12	1.02	27.48	51.57	12.52	9.92
DF-5-B	6.53	8.72	5.55	0.12	1.00	26.68	38.98	34.35	9.72
DF-5-C	6.11	5.56	6.70	0.06	0.52	19.04	29.31	51.65	10.1
DF-6-A	7.55	9.28	22.3	0.16	1.37	28.64	54.85	16.52	9.99
DF-6-B	7.64	8.80	20.7	0.15	1.46	28.59	53.20	18.21	11.4
平均 ± SD	6.67 ± 0.85	5.76 ± 3.18	13.8 ± 7.38	0.10 ± 0.04	1.02 ± 0.46	21.39 ± 7.49	36.26 ± 12.06	42.35 ± 18.98	12.0 ± 2.20

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A2 茅尾海红树林表层沉积物主要理化参数

A2 Main physicochemical parameters of the surface sediments in the mangrove of Maowei Sea

样品编号	pH值	电导率/(mS·cm⁻¹)	盐度	TN含量/%	TOC含量/%	黏土占比/%	粉砂占比/%	砂占比/%	C/N摩尔比
MW-1-A	5.31	2.95	3.65	0.23	4.26	17.76	28.14	54.11	21.6
MW-1-B	4.40	2.14	3.65	0.06	1.53	13.19	23.95	62.87	29.8
MW-2-A	2.88	2.23	3.01	0.04	0.56	20.65	35.24	44.12	16.3
MW-2-B	3.90	1.31	3.01	0.06	0.85	8.11	13.05	78.84	16.5
MW-3-A	5.26	1.43	3.07	0.11	1.64	14.34	23.46	62.20	17.4
MW-3-B	4.74	1.22	3.07	0.06	1.10	19.37	34.16	46.48	21.4
MW-4-A	5.24	3.93	11.4	0.17	3.68	19.49	38.47	42.04	25.3
MW-4-B	6.31	3.53	11.4	0.08	1.68	16.92	29.62	53.45	24.5
MW-5-A	5.16	4.00	20.6	0.07	1.24	19.21	41.37	39.42	20.7
MW-5-B	5.24	5.34	20.6	0.13	2.64	24.55	50.85	24.61	23.7
平均 ± SD	4.84 ± 0.94	2.81 ± 1.38	8.35 ± 7.27	0.10 ± 0.06	1.92 ± 1.23	17.36 ± 4.56	31.83 ± 10.63	50.81 ± 15.04	21.7 ± 4.30

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A3 大风江入海口红树林表层沉积物的Fe_R、Fe-OC、δ¹³C等参数

A3 Parameters such as Fe_R, Fe-OC, δ¹³C of the surface sediments of mangrove in the estuary of Dafeng River

样品编号	Fe_R/(mg·g⁻¹)	Fe-OC含量/%	Fe-OC∶Fe摩尔比	f_Fe-OC/%	δ¹³C_bulk/‰	δ¹³C_non-FeOC/‰	δ¹³C_Fe-OC/‰	Δδ¹³C/‰
DF-1-A	21.6	0.17	0.36	10.7	−23.41	−24.10	−16.36	7.74
DF-2-A	17.9	0.12	0.33	15.9	−25.22	−25.68	−22.47	3.21
DF-3-A	9.05	0.11	0.56	12.4	−24.93	−25.30	−17.70	7.60
DF-3-B	12.6	0.27	0.98	16.9	−27.25	−27.73	−24.88	2.85
DF-3-C	11.2	0.15	0.61	12.9	−26.60	−27.13	−21.25	5.88
DF-4-A	12.8	0.12	0.39	17.6	−24.40	−24.91	−20.68	4.24
DF-4-B	5.47	0.07	0.64	13.6	−25.66	−26.26	−22.80	3.45
DF-4-C	11.2	0.14	0.59	16.6	−25.75	−26.13	−24.09	2.05
DF-5-A	16.3	0.15	0.41	17.4	−24.84	−25.16	−22.41	2.75
DF-5-B	9.86	0.22	1.13	24.0	−25.45	−25.97	−22.40	3.57
DF-5-C	9.77	0.11	0.55	21.2	−25.52	−25.76	−24.68	1.08
DF-6-A	14.8	0.21	0.65	15.1	−24.81	−24.48	−26.07	−1.59
DF-6-B	13.6	0.23	0.79	16.6	−25.05	−24.52	−27.46	−2.94
平均 ± SD	12.8 ± 4.19	0.16 ± 0.07	0.61 ± 0.27	16.2 ± 3.58	−25.30 ± 0.93	−25.63 ± 1.03	−22.56 ± 3.05	3.07 ± 3.03

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A4 茅尾海红树林表层沉积物的Fe_R、Fe-OC、δ¹³C等参数

A4 Parameters such as FeR, Fe-OC, δ¹³C of the surface sediments of mangrove in Maowei Sea

样品编号	Fe_R/(mg·g⁻¹)	Fe-OC含量/%	Fe-OC∶Fe摩尔比	f_Fe-OC/%	δ¹³C_bulk/‰	δ¹³C_non-FeOC/‰	δ¹³C_Fe-OC/‰	Δδ¹³C/‰
MW-1-A	10.5	0.16	0.73	3.87	−	−	−	−
MW-1-B	6.77	0.06	0.41	3.92	−26.99	−27.41	−25.66	1.75
MW-2-A	5.35	0.07	0.58	12.0	−	−	−	−
MW−2-B	5.73	0.18	1.43	20.8	−25.89	−26.60	−23.23	3.37
MW-3-A	16.7	0.18	0.50	11.0	−	−	−	−
MW-3-B	14.9	0.15	0.47	13.7	−26.45	−26.75	−24.57	2.18
MW-4-A	15.1	0.18	0.56	4.95	−	−	−	−
MW-4-B	13.0	0.29	1.02	16.9	−26.34	−26.79	−24.11	2.68
MW-5-A	22.4	0.16	0.33	12.8	−	−	−	−
MW-5-B	23.1	0.24	0.48	9.01	−26.44	−26.38	−27.04	−0.65
平均 ± SD	13.4 ± 6.39	0.17 ± 0.07	0.65 ± 0.33	10.9 ± 5.62	−26.42 ± 0.37	−26.78 ± 0.36	−24.92 ± 1.39	1.87 ± 1.44
注：“−”表示无数据。

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A5 大风江入海口与茅尾海表层沉积物中铁化合物的穆斯堡尔谱参数

A5 Mössbauer spectral parameters of iron compounds in surface sediments in the estuary of Dafeng River and Mawei Sea

样品编号	铁的化学态	相对占比/%	IS/(mm·s⁻¹)	QS/(mm·s⁻¹)	Fe²⁺/Fe³⁺
DF-1-A	para-Fe²⁺ para-Fe³⁺	16.20 83.80	1.099 ± 0.018 0.368 ± 0.003	2.922 ± 0.034 0.642 ± 0.005	0.193
DF-2-A	para-Fe²⁺ para-Fe³⁺	13.85 86.15	1.085 ± 0.020 0.368 ± 0.003	2.809 ± 0.040 0.621 ± 0.004	0.161
DF-3-A	para-Fe²⁺ para-Fe³⁺	13.53 86.47	1.109 ± 0.020 0.350 ± 0.002	2.625 ± 0.039 0.627 ± 0.003	0.156
DF-3-B	para-Fe²⁺ para-Fe³⁺	13.19 86.81	1.062 ± 0.022 0.358 ± 0.003	2.534 ± 0.044 0.625 ± 0.005	0.152
DF-3-C	para-Fe²⁺ para-Fe³⁺	16.98 83.02	1.045 ± 0.036 0.354 ± 0.005	2.498 ± 0.071 0.591 ± 0.009	0.205
DF-4-A	para-Fe²⁺ para-Fe³⁺	12.73 87.27	1.270 ± 0.015 0.337 ± 0.003	2.242 ± 0.031 0.682 ± 0.006	0.146
DF-4-B	para-Fe²⁺ para-Fe³⁺	14.67 85.33	1.066 ± 0.034 0.354 ± 0.004	2.634 ± 0.068 0.628 ± 0.007	0.172
DF-4-C	para-Fe²⁺ para-Fe³⁺	14.93 85.07	1.081 ± 0.007 0.356 ± 0.001	2.632 ± 0.013 0.633 ± 0.002	0.176
DF-5-A	para-Fe²⁺ para-Fe³⁺	17.08 82.92	1.066 ± 0.027 0.363 ± 0.004	2.695 ± 0.054 0.606 ± 0.007	0.206
DF-5-B	para-Fe²⁺ para-Fe³⁺	10.39 89.61	1.253 ± 0.016 0.332 ± 0.003	2.228 ± 0.032 0.677 ± 0.006	0.116
DF-5-C	para-Fe²⁺ para-Fe³⁺	20.62 79.38	1.241 ± 0.030 0.336 ± 0.005	2.218 ± 0.060 0.653 ± 0.011	0.260
DF-6-A	para-Fe²⁺ para-Fe³⁺	12.86 87.14	1.264 ± 0.008 0.326 ±0.003	2.259 ± 0.016 0.704 ± 0.005	0.148
DF-6-B	para-Fe²⁺ para-Fe³⁺	10.28 89.72	1.291 ± 0.009 0.334 ± 0.003	2.291 ± 0.018 0.690 ± 0.005	0.115
MW-1-A	para-Fe²⁺ para-Fe³⁺	8.44 91.56	1.293 ± 0.022 0.348 ± 0.004	2.282 ± 0.045 0.671 ± 0.007	0.092
MW-3-A	para-Fe²⁺ para-Fe³⁺	0.00 100.00	未检测到 0.356 ± 0.004	未检测到 0.869 ± 0.006	0.000
MW-4-A	para-Fe²⁺ para-Fe³⁺	9.17 90.83	1.055 ± 0.016 0.368 ± 0.002	2.647 ± 0.033 0.642 ± 0.003	0.101
MW-5-A	para-Fe²⁺ para-Fe³⁺	9.02 90.98	1.093 ± 0.038 0.350 ± 0.003	2.792 ± 0.075 0.645 ± 0.005	0.099

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