聚磷酸铵在紫色土壤中的吸附-解吸特征

doi:10.3969/j.issn.1004-1524.2023.02.18

浙江农业学报 ›› 2023, Vol. 35 ›› Issue (2): 403-416.DOI: 10.3969/j.issn.1004-1524.2023.02.18

聚磷酸铵在紫色土壤中的吸附-解吸特征

袁太艳¹(), 严正娟¹^,^*(), 黄成东², 张志业¹, 王辛龙¹

1.四川大学化学工程学院,磷资源综合利用与清洁加工教育部工程研究中心,四川成都 610065
2.中国农业大学资源与环境学院,国家农业绿色发展研究院,植物-土壤相互作用教育部重点实验室,北京 100193

收稿日期:2022-01-29 出版日期:2023-02-25 发布日期:2023-03-14
通讯作者: 严正娟
作者简介:*严正娟,E-mail: zjyan@scu.edu.cn
袁太艳(1997—),女,贵州毕节人,硕士研究生,主要从事土壤肥料与磷资源利用方面的研究。E-mail: 961731822@qq.com
基金资助:
国家自然科学基金(32172677)

Adsorption-desorption characteristics of ammonium polyphosphate in purple soils

YUAN Taiyan¹(), YAN Zhengjuan¹^,^*(), HUANG Chengdong², ZHANG Zhiye¹, WANG Xinlong¹

1. Engineering Research Center of Comprehensive Utilization and Clean Processing of Phosphorus Resources of Ministry of Education, School of Chemical Engineering, Sichuan University, Chengdu 610065, China
2. National Institute of Agricultural Green Development, Ministry of Education Key Laboratory of Plant-Soil Interaction, College of Resources and Environmental Sciences, China Agricultural University, Beijing 100193, China

Received:2022-01-29 Online:2023-02-25 Published:2023-03-14
Contact: YAN Zhengjuan

摘要/Abstract

摘要：

以两种聚磷酸铵(APP1,低聚合度;APP2,高聚合度)为研究对象,基于吸附-解吸试验,运用等温方程模型,并结合不同聚合度的磷素形态分析,探讨水溶性聚磷酸铵(APP)在典型酸性和石灰性紫色土壤中的吸附-解吸特征及其与磷酸一铵(MAP)的差异,为其在紫色土壤中的合理高效利用提供理论依据。结果表明,随着磷添加量(1~300 mg·L^-1)的增加,酸性紫色土壤对APP的吸附呈先增加后降低的趋势,而石灰性紫色土壤对APP的吸附则始终呈上升趋势。当磷添加量为1~100 mg·L^-1,酸性紫色土壤对APP1和APP2的吸附分别更符合Langmuir方程(R²=0.961)和Freundlich方程(R²=0.947),石灰性紫色土壤对两种APP的吸附均符合Freundlich方程(R²分别为0.995和0.950)。两种紫色土壤对APP的吸附均以聚磷酸盐为主,且APP1和APP2中焦磷酸盐对磷吸附的贡献率分别超过76%和36%。在较高磷添加量下,APP中正磷酸盐在酸性紫色土壤中出现负吸附。同时,在两种紫色土壤中,APP中正磷酸盐的解吸率均高于聚磷酸盐,在酸性紫色土壤中正磷酸盐的解吸率在较高磷吸附条件下甚至超过100%。与MAP相比,在较低磷添加量下,两种紫色土壤对APP的吸附量更大。APP增加了吸附平衡液中Fe、Al和溶解有机碳的含量,但会降低Ca的含量。综上,含多种形态磷的APP施入土壤后,并不是降低了其本身被土壤的吸附固定,而是通过促进土壤中原有正磷酸盐的释放,进而保持正磷酸盐的有效供应。此外,APP自身磷素形态的分布特点也决定了其施入土壤后的有效性。

关键词: 紫色土壤, 聚磷酸铵, 吸附, 解吸, 磷形态

Abstract:

Ammonium polyphosphate (APP) of APP1 (low polymerization degree) and APP2 (high polymerization degree) were used as the research objects. Based on the adsorption-desorption test, the adsorption and desorption characteristics of APP in typical acid and calcareous purple soils were investigated by using isothermal equation model, combined with the analysis of phosphorus (P) forms in the equilibrium solution in comparison with monoammonium phosphate (MAP), in order to provide theoretical basis for efficient utilization of APP in purple soils. The results showed that with the increase of P addition (1-300 mg·L^-1), the adsorption of APP by acid purple soil increased first and then decreased, while always increased by calcareous purple soil. When the P addition was 1-100 mg·L^-1, the adsorption of APP1 and APP2 by acid purple soil better fitted the Langmuir equation (R²=0.961) and Freundlich equation (R²=0.947), respectively, while the adsorption of APP by calcareous purple soil fitted the Freundlich equation (R² of 0.995, 0.950, respectively). Two purple soils dominantly absorbed the polyphosphate (poly-P) in the APPs, especially for pyrophosphate (pyro-P), and the contribution rate of pyro-P in the APP1 and APP2 to P adsorption exceeded 76% and 36%, respectively. Under higher P addition, the negative adsorption phenomenon occurred for the adsorption of orthophosphate (ortho-P) in the APP by acid purple soil. Meanwhile, in the two purple soils, the desorption rate of ortho-P in the APP was higher than that of poly-P, and the desorption rate of ortho-P in acid purple soil with high adsorbed P even exceeded 100%. Under low P addition, the adsorption amount of APP was higher than that of MAP by two purple soils. APP increased the contents of Fe, Al and dissolved organic carbon, while reduced the content of Ca in the adsorption equilibrium solutions. In conclusion, APP with various P forms maintained ortho-P supply via promoting the ortho-P release from the soil, but not via reducing its adsorption by the soil. In addition, the distribution of P forms in the APP also determined its availability in the soil.

Key words: purple soil, ammonium polyphosphate, adsorption, desorption, phosphorus forms

中图分类号:

S143.2

袁太艳, 严正娟, 黄成东, 张志业, 王辛龙. 聚磷酸铵在紫色土壤中的吸附-解吸特征[J]. 浙江农业学报, 2023, 35(2): 403-416.

YUAN Taiyan, YAN Zhengjuan, HUANG Chengdong, ZHANG Zhiye, WANG Xinlong. Adsorption-desorption characteristics of ammonium polyphosphate in purple soils[J]. Acta Agriculturae Zhejiangensis, 2023, 35(2): 403-416.

图/表 13

表1 供试土壤的基本性质

Table 1 Properties of soils used in experiment

指标 Index	酸性紫色土壤 Acid purple soil	石灰性紫色土壤 Calcareous purple soil
pH	4.36	8.05
CaCO₃/(g·kg^-1)	—	39.08
有机质	4.49	8.73
Organic matter/(g·kg^-1)
全磷Total P/(g·kg^-1)	0.46	0.85
全氮Total N/(g·kg^-1)	0.48	0.86
有效磷Olsen-P/(mg·kg^-1)	85.4	7.2
黏粒	37.2	196.8
Clay/(<0.002 mm,g·kg^-1)
游离态铁氧化物	1.95	4.63
Free Fe oxides/(g·kg^-1)
游离态铝氧化物	4.22	2.54
Free Al oxides /(g·kg^-1)
无定型铁氧化物	0.11	0.11
Amorphous Fe oxides/(g·kg^-1)
无定型铝氧化物	0.12	0.12
Amorphous Al oxides/(g·kg^-1)

表2 供试磷源的分子量、pH值和磷形态分布

Table 2 Molecular weight, pH and mass fraction distribution of different P forms used in experiment

磷源 P source	分子量 Molecular weight	pH	磷形态分布Mass fraction distribution of P forms/%
磷源 P source	分子量 Molecular weight	pH	P1	P2	P3	P4	P5	P6	P7
MAP	115.0	5.4	100.00	—	—	—	—	—	—
APP1	168.3	6.5	41.99	58.01	—	—	—	—	—
APP2	272.6	7.0	23.59	30.14	22.23	12.87	6.57	2.86	1.75

图1 酸性紫色土壤(A)和石灰性紫色土壤(B)对不同磷源全磷的吸附等温曲线

Fig.1 Adsorption isotherm of total P of different P sources in acid purple soil (A) and calcareous purple soil (B)

图2 酸性紫色土壤(A)和石灰性紫色土壤(B)对不同磷源的全磷吸附率

Fig.2 Adsorption rate of total P of different P sources by acid purple soil (A) and calcareous purple soil (B)

表3 不同磷源处理下土壤中磷素(1~100 mg·L-1)吸附的Langmuir和Freundlich方程拟合结果

Table 3 Fitting result of P (1-100 mg··L-1) sorption of soils under different phosphorus sources by Langmuir and Freundlich equations

土壤 Soil	磷源 P source	Langmuir方程参数 Parameters of Langmuir equation					Freundlich方程参数 Parameters of Freundlich equation
土壤 Soil	磷源 P source	S_max	K_L	R²	DPS	PBC	K_F	n	R²
酸性紫色土壤	MAP	337	0.069	0.860	20.24	23.22	47.66	0.395	0.986
Acid purple soil	APP1	499	0.104	0.961	14.63	51.95	61.89	0.499	0.872
	APP2	532	0.079	0.891	13.84	42.26	72.99	0.423	0.947
石灰性紫色土壤	MAP	494	0.069	0.831	1.437	34.25	91.87	0.289	0.922
Calcareous purple soil	APP1	2664	0.032	0.680	—	84.55	94.82	0.749	0.995
	APP2	3507	0.023	0.213	—	81.05	112.84	0.693	0.950

图3 APP中不同形态磷对紫色土壤磷素吸附的贡献正磷酸盐,n=1;聚磷酸盐,n≥2。下同。A,APP1,酸性紫色土壤;B,APP2,酸性紫色土壤;C,APP1,石灰性紫色土壤;D,APP2,石灰性紫色土壤。

Fig.3 Contribution of different forms of P in ammonium polyphosphate (APP) to P adsorption in purple soil Ortho-P, n=1; Poly-P, n≥2. The same as below.A, APP1, acid purple soil; B, APP2, acid purple soil; C, APP1, calcareous purple soil; D, APP2, calcareous purple soil.

图4 不同浓度APP在紫色土壤中吸附平衡时的磷素去向 A,APP1,酸性紫色土壤;B,APP2,酸性紫色土壤;C,APP1,石灰性紫色土壤;D,APP2,石灰性紫色土壤。a,吸附前;b,吸附后。P1,正磷酸盐;P2,焦磷酸盐;P3,三聚磷酸盐;P4,四聚磷酸盐;P5,五聚磷酸盐;P6,六聚磷酸盐;P7,七聚磷酸盐。

Fig.4 P fate at adsorption equilibrium of ammonium polyphosphate (APP) in purple soil A, APP1, acid purple soil; B, APP2, acid purple soil; C, APP1, calcareous purple soil; D, APP2, calcareous purple soil. a, Before adsorption; b, After adsorption. P1, Orthophosphate; P2, Pyrophosphate; P3, Tripolyphosphate; P4, Tetraphosphate; P5, Pentaphosphate; P6, Hexaphosphate; P7, Heptaphosphate.

图5 不同磷源对酸性紫色土壤(A)和石灰性紫色土壤(B)吸附平衡液pH值的影响相同磷添加量下,柱上无相同字母的表示差异显著(P<0.05)。下同。

Fig.5 Effects of different P sources on pH of adsorption equilibration of acid purple soil (A) and calcareous purple soil (B) Bars marked without the same letters indicated significant difference at P<0.05 under the same P addition amount. The same as below.

图6 不同磷源下酸性紫色土壤(A、C、E)和石灰性紫色土壤(B、D、F)磷素吸附平衡液中的Ca(A、B)、Fe(C、D)、Al(E、F)含量

Fig.6 Concentrations of Ca (A, B), Fe (C, D) and Al (E, F) in adsorption equilibration solutions of acid purple soil (A, C, E) and calcareous purple soil (B, D, F) with different P sources

图7 不同磷源下酸性紫色土壤(A)和石灰性紫色土壤(B)磷素吸附平衡液中的溶解有机碳(DOC)含量

Fig.7 Concentrations of dissolved organic carbon (DOC) in adsorption equilibration solutions of acid purple soil (A) and calcareous purple soil (B) with different P sources

图8 不同磷源下酸性紫色土壤(A)和石灰性紫色土壤(B)上全磷的解吸等温曲线

Fig.8 Desorption isotherms of total P on acid purple soil (A) and calcareous purple soil (B) of total P in different soils with different P sources

图9 APP1(A、C)和APP2(B、D)中不同形态磷在酸性紫色土壤中的解吸量(A、B)和解吸率(C、D)

Fig.9 Desorption amount (A, B) and rate (C, D) of different forms of P in APP1 (A, C) and APP2 (B, D) in acid purple soil

图10 APP1(A、C)和APP2(B、D)中不同形态磷在石灰性紫色土壤中的解吸量(A、B)和解吸率(C、D)

Fig.10 Desorption amount (A, B) and rate (C, D) of different forms of P in APP1 (A, C) and APP2 (B, D) in calcareous purple soil

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聚磷酸铵在紫色土壤中的吸附-解吸特征

Adsorption-desorption characteristics of ammonium polyphosphate in purple soils

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