广西象州与横县碳酸盐岩分布区土壤中Cd形态分布特征及影响因素

现代地质 ›› 2017, Vol. 31 ›› Issue (02): 374-385.

广西象州与横县碳酸盐岩分布区土壤中Cd形态分布特征及影响因素

刘旭¹(), 顾秋蓓¹, 杨琼¹, 余涛¹(), 张起钻²

1.中国地质大学(北京) 地球科学与资源学院,北京 100083
2.广西壮族自治区地质矿产勘查开发局,广西南宁 530023

收稿日期:2016-10-16 修回日期:2017-02-18 出版日期:2017-04-10 发布日期:2017-04-25
通讯作者: 余涛,男,副研究员,1979年出生,地球化学专业,主要从事环境地球化学、生态地球化学、勘查地球化学和土地质量地球化学评价等方面的研究工作。Email:yutao@cugb.edu.cn。
作者简介:刘旭,男,硕士研究生,1993年出生,地球化学专业,主要从事环境地球化学研究。Email:liuxunm@outlook.com。
基金资助:
广西壮族自治区国土资源厅“广西中东部地区土壤硒元素和重金属元素地球化学研究”(桂国土资发[2015]44号);中国地质调查局项目“湘鄂重金属高背景区1∶5万土地质量地球化学调查与风险评价”(DD20160323)

Distribution and Influencing Factors of Cadmium Geochemical Fractions of Soils at Carbonate Covering Area in Hengxian and Xiangzhou of Guangxi

LIU Xu¹(), GU Qiubei¹, YANG Qiong¹, YU Tao¹(), ZHANG Qizuan²

1. School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China
2. Guangxi Bureau of Geology and Mineral Prospecting and Exploitation, Nanning, Guangxi 530023, China

Received:2016-10-16 Revised:2017-02-18 Online:2017-04-10 Published:2017-04-25

摘要/Abstract

摘要：

广西壮族自治区碳酸盐岩分布面积为96 372 km²,约占全区陆地国土面积的40.7%。由碳酸盐岩风化形成的土壤中Cd、Pb、Hg等重金属元素普遍富集。初步评价发现,农作物籽实对Cd的吸收量与土壤Cd含量无对应关系,农作物Cd超标多出现在土壤Cd含量较低的地区。进一步研究发现,Cd高含量的土壤中普遍含有铝土矿、Fe-Mn结核等颗粒。为了探索土壤中Cd存在形态及其影响因素,选择了含铝土矿和铁锰结核的横县土壤和无铝土矿与铁锰结核的象州土壤,系统研究了土壤Cd形态差异及其影响因素。结果表明:(1)象州土壤中Cd主要以活动态形式存在,生物可利用性高,横县土壤中Cd主要以稳定态形式存在,生物可利用性低。(2)pH值为6.0是象州土壤Cd活动态含量的突变点,pH值在6.0处含量达到最大值;而在横县,pH降低使活动态Cd比例增加。(3)象州土壤中活动态Cd随有机质增加而增加,表明Cd被有机质弱吸附;而横县土壤有机质含量与Cd形态无明显相关性。(4)由铝土矿导致的土壤高Cd含量,多以残渣态形式存在,不会对动植物造成危害。

关键词: 广西, 碳酸盐岩, 镉形态, pH值, 有机质

Abstract:

The carbonate covering area is about 96,372 km², accounting for about 40.7% of district land area in Guangxi Zhuang Autonomous Region. The heavy metals in soil formed from the carbonate weathering were enriched commonly, such as cadmium (Cd), lead (Pb) and mercury (Hg). Preliminary evaluation results showed that there was no corresponding relation between Cd uptake of crops and Cd content in soil. Crops which exceed food safety standards always grew in the soil with low Cd content.Soil with high Cd content generally contained bauxite, Fe-Mn nodules and other particles.In order to discuss factors affecting geochemical fractions of Cadmium, we determined geochemical fractions of cadmium and other soil properties in two study areas in relation to bauxite and Fe-Mn nodules. Soils in the Hengxian area were with bauxite and Fe-Mn nodules. Soils in the Xiangzhou area were without bauxite and Fe-Mn nodules.The results show that: (1) In Xiangzhou area, the Cd content of soil was mainly bounded to mobile fraction and the bioavailability of Cd was high. In Hengxian area, Cd was mainly bounded to residue fraction, the bioavailability was low.(2) Soil pH and organic matter were important factors controlling the Cd mobility.Soil pH value 6.0 is the abrupt change point of the Cd mobility,contents of ion-exchange Cd reached maximum in soil pH value 6.0 in Xiangzhou soils. The percentage of mobile fraction Cd was increasing with soil pH decreasing in Hengxian soils. (3) Cd in mobile fraction was correlated positively with organic matter in Xiangzhou soils, which indicated that Cd is weakly adsorbed by organic matter in soil. Cd fraction has no obvious correlation with organic matter in Hengxian soil. (4) The Cd content of soil with bauxite was high, which occurred in the residual fraction in Hengxian. So, it was not harmful to animals or plants.

Key words: Guangxi, carbonate, cadmium fractions, pH, organic matter

中图分类号:

P595
X142

刘旭, 顾秋蓓, 杨琼, 余涛, 张起钻. 广西象州与横县碳酸盐岩分布区土壤中Cd形态分布特征及影响因素[J]. 现代地质, 2017, 31(02): 374-385.

LIU Xu, GU Qiubei, YANG Qiong, YU Tao, ZHANG Qizuan. Distribution and Influencing Factors of Cadmium Geochemical Fractions of Soils at Carbonate Covering Area in Hengxian and Xiangzhou of Guangxi[J]. Geoscience, 2017, 31(02): 374-385.

图/表 19

图1 横县研究区原生铝土矿与土壤中铝土矿照片

Fig.1 The picture of primary bauxite and the bauxite in soil in Hengxian

表1 横县土壤不同粒径铝土矿、铁锰结核比例

Table 1 The different particle size of bauxite, Fe-Mn nodules of soil in Hengxian

目数/目	>10	10~20	20~40	40~60	60~80	80~100	100~120	<120
比例/%	20.44	27.46	11.09	5.61	3.49	2.99	2.08	26.84

图2 研究区位置图

Fig.2 Location of the study area in Guangxi

表2 Cd不同形态分析检出限

Table 2 Requirements of detection limits to various fractions of Cd

元素	检出限/(mg/kg)
元素	水溶态	离子交换态	碳酸盐态	腐殖酸态	铁锰氧化态	强有机态	残渣态
Cd	0.005	0.02	0.02	0.02	0.02	0.02	0.03

表3 Cd形态分析监控限

Table 3 Analyzing inspection limits

含量范围/(mg/kg)	相对双差(RD)/%
≤3倍方法检出限	80
>3倍方法检出限	60

表4 日常分析准确度、精密度要求

Table 4 The accuracy and precision requirements of daily analysis

含量范围	准确度		精密度
含量范围	ΔlgC(GBW)= $l g C i ˉ - l g C s$ )		λ= $∑ i = 1 n (C i - C s) 2 4 - 1$
检出限3倍以内	≤0.12	0.17
检出限3倍以上	≤0.10	0.15
1%~5%	≤0.07	0.10
>5%	≤0.05	0.08

表4 日常分析准确度、精密度要求

Table 4 The accuracy and precision requirements of daily analysis

含量范围	准确度		精密度
含量范围	ΔlgC(GBW)= $l g C i ˉ - l g C s$ )		λ= $∑ i = 1 n (C i - C s) 2 4 - 1$
检出限3倍以内	≤0.12	0.17
检出限3倍以上	≤0.10	0.15
1%~5%	≤0.07	0.10
>5%	≤0.05	0.08

表5 土壤Cd形态、pH和TOC的准确度与精密度

Table 5 The accuracy and precision of Cd fractions,pH and TOC of soil

指标	Cd形态							pH	TOC
指标	水溶态	离子态	碳酸盐态	腐殖酸态	铁锰态	强有机态	残渣态	pH	TOC
准确度/%				4.54				0.01	0.02
精密度/%	0.00	15.22	15.96	14.89	10.68	9.44	8.95	0.00	0.03

表6 横县、象州研究区土壤Cd不同形态含量与比例

Table 6 The content and percentages of different Cd fractions in Hengxian and Xiangzhou soil

地区	平均值	水溶态	离子交换态	碳酸盐结合态	腐殖酸结合态	铁锰氧化态	强有机结合态	残渣态	各态加和
横县	含量/(mg/kg)	0.011	0.079	0.036	0.037	0.076	0.01	0.391	0.661
n=30	比例/%	1.66	11.87	5.47	5.58	11.50	4.73	59.18	100.00
象州	含量/(mg/kg)	0.001	0.05	0.024	0.026	0.022	0.012	0.028	0.164
n=30	比例/%	0.61	31.01	14.63	15.80	13.47	7.47	17.02	100.00

图3 象州土壤Cd不同形态占总量比值

Fig.3 The percentages of different Cd fractions in Xiangzhou soil

图4 横县土壤Cd不同形态占总量比值图

Fig.4 The percentages of different Cd fractions in Hengxian soil

图5 横县土壤各形态Cd所占比例与Cd总量的相关性图

Fig.5 The correlations between different Cd fractions contents and total Cd in soil of Hengxian

图6 象州土壤各形态Cd所占比例与Cd总量的相关性图

Fig.6 The correlations between different Cd fractions contents and total Cd in soil of Xiangzhou

图7 横县土壤不同pH值下Cd活动态、稳定态占总量比例对比图

Fig.7 The comparison of different Cd fractions content with soil pH changing in Hengxian

图8 象州土壤离子交换态Cd随土壤pH值变化趋势图

Fig.8 The trend of Cd in ion exchangeable fraction content with soil pH changing in Xiangzhou

图9 象州土壤不同pH值下Cd活动态、稳定态占总量比例对比图

Fig.9 The comparison chart of different Cd fractions content with soil pH changing in Xiangzhou

图10 象州与横县Cd总量随TOC值变化趋势图

Fig.10 The trend of Cd total content with TOC changing in Xiangzhou and Hengxian

图11 象州Cd含量随土壤TOC值变化趋势图

Fig.11 The trend of different Cd fractions content with TOC changing in Xiangzhou

图12 横县Cd含量随土壤TOC值变化趋势图在

Fig.12 The trend of different Cd fractions content with TOC changing in Hengxian

图13 横县残渣态Cd随土壤pH值变化趋势图

Fig.13 The trend of Cd in residual fraction content with soil pH changing in Hengxian

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