钛石膏土壤化利用的安全风险及前景分析

云易; 王港; 苏海锋

doi:10.7513/j.issn.1004-7638.2024.03.013

钛石膏土壤化利用的安全风险及前景分析

doi: 10.7513/j.issn.1004-7638.2024.03.013

云易^{1, 2,},
王港²,
苏海锋^2, ,

1.
中国科学院大学资源与环境学院, 北京101408
2.
中国科学院重庆绿色智能技术研究院, 重庆400714

基金项目: 国土资源部自然资源部退化及未利用土地整治工程项目（SXDJ-202425）。

详细信息

作者简介:
云易，1997年出生，河南郑州人，硕士研究生，研究方向：土壤与固废利用，E-mail: yunyi20@mails.ucas.ac.cn

通讯作者:
苏海锋，博士，硕导，主要研究方向：土壤修复，固废利用，E-mail：suhaifeng@cigit.ac.cn

中图分类号: X788,S156
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出版历程
- 收稿日期: 2024-03-06
- 刊出日期: 2024-07-02

Safety risk and prospect analysis of titanium gypsum on soil utilization

Yun Yi^{1, 2
,},
Wang Gang²,
Su Haifeng^{2
, ,}

1.
College of Resources and Environment, University of Chinese Academy of Sciences, Beijing 101408, China
2.
Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China

摘要

摘要: 目前，钛石膏的资源化利用率不足10%，缺乏可大规模消纳的应用领域，而土壤化可能是一个重要的方向。提出将钛石膏作为土壤化的资源利用途径，分析其作为土壤资源化利用时面临的安全性问题，探究其用作土壤的基本性质及安全风险。通过浸出毒性对钛石膏进行安全风险评价，分析其理化性质及在土壤利用方面的可行性，以及通过内梅罗指数（P）等方法探究其土壤风险与营养性。研究结果表明，钛石膏的理化性质适宜将其作为土壤母质进一步资源化利用，在国家农用土与绿化土标准规定的8种重金属限制范围内没有严重的环境风险，但钒等部分重金属含量超出了绿化用有机基质的标准，可能成为新的污染物。鉴于以上结果，可以考虑在经过营养性等改良、排除重金属污染风险后，作为土壤化进行资源化利用。为钛石膏资源化利用作土壤资源，进而实现大规模消纳提供了参考。
- 钛石膏 /
- 固体废物 /
- 浸出毒性 /
- 土壤重金属 /
- 资源化利用 /
- 安全风险
Abstract: Up to now, the resource utilization rate of titanium gypsum is less than 10%, and there is no application field that can be consumed on a large scale, and soilization may be an important direction. In this paper, titanium gypsum was proposed as a soil resource, and the safety problems faced by it as a soil resource utilization were analyzed, and the basic properties and safety risks of it as soil were explored. The safety risk of titanium gypsum was evaluated by leaching toxicity, its physicochemical properties and feasibility in soil utilization were also analyzed, and its soil risk and nutritivity were investigated by Nemero index (P). The results show that the physical and chemical properties of titanium gypsum are suitable for further resource utilization as soil parent material, and there is no serious environmental risk within the limit range of 8 heavy metals stipulated in the national agricultural soil and green soil standards. However, the content of heavy metals such as vanadium exceeds the standard of organic substrates used in greening and may become new pollutants. In view of the above results, it can be considered as a soil resource utilization after the nutritional improvement and the elimination of heavy metal pollution risk. This study provides a reference for the utilization of titanium gypsum as soil resources and the direction of large-scale consumption.
- titanium gypsum /
- solid waste /
- leaching toxicity /
- soil heavy metals /
- resource utilization /
- security risk

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图 1 钛石膏样品

(a)干样； (b) 湿样　　

Figure 1. Titanium gypsum samples

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图 3 钛石膏重金属含量与《农用地土壤污染风险管控标准》管控值对照

左侧纵坐标指Pb、Cr、Ni、Cu、Zn含量；右侧纵坐标指Cd 、Hg 、As含量

Figure 3. Comparision of the heavy metal content of titanium gypsum with the control value of “Agricultural land soil pollution risk control standard”

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图 4 钛石膏重金属含量与《绿化种植土壤》Ⅰ、Ⅱ级技术要求值对照

左侧纵坐标指Pb、Cr、As、Ni、Cu、Zn含量；右侧纵坐标指Cd、Hg含量

Figure 4. Comparision of the heavy metal content of titanium gypsum with the technical requirements of grade I and II of “Greening Planting Soil”

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图 2 钛石膏雨水连续静态浸出毒性占危险废物鉴别标准限值的比例

注：经检测，Cd、Hg、Pb的浸出毒性含量均低于检出限，图中均用0表示其含量。

Figure 2. The proportion of continuous static leaching toxicity of titanium gypsum by rainwater to the standard limit for identification of hazardous waste

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图 5 钛石膏的重金属污染单因子指数、内梅罗指数与《土壤环境监测技术规范》中的土壤质量评价等级对照

Figure 5. Comparison of single factor index and Nemerow index of heavy metal pollution of titanium gypsum with soil quality evaluation grade in “Technical specification for soil environmental monitoring”

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图 6 钛石膏与全国第二次土壤普查养分分级标准的养分对照

Figure 6. Nutrient comparison between titanium gypsum and nutrient classification standard of the second national soil survey

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表 1 雨水连续静态浸出安全性试验的试验组设置

Table 1. Experimental group setting for continuous static leaching safety test of rainwater

编号	浸提剂pH	温度/ ℃
1	5	30
2	5	35
3	5	40
4	5	较高的非恒温室温
5	6	30
6	6	35
7	6	40
8	6	较高的非恒温室温
9	7	30
10	7	35
11	7	40
12	7	较高的非恒温室温

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表 2 钛石膏的浸出毒性与相关标准限值对照

Table 2. Comparision of leaching toxicity of titanium gypsum with the relevant standard limits

硫酸硝酸法				水平振荡法
危害成分	浸出液中危害成分含量/(mg·L⁻¹)	危险废物判定标准浓度限值/(mg·L⁻¹)	占比/%	危害成分	浸出液中危害成分含量/(mg·L⁻¹)	第I类一般工业固体废物判定标准浓度限值/(mg·L⁻¹)	占比/%
总Cu	*2.5×10⁻³	100	0.00	总Cu	1.06×10⁻³	1	0.11
总Pb	*4.2×10⁻³	5	0.00	总Pb	1.04×10⁻³	1	0.10
总Zn	0.181	100	0.18	总Zn	4.79×10⁻²	5	0.96
总Cd	*1.2×10⁻³	1	0.00	总Cd	1.2×10⁻⁴	0.1	0.12
总Ni	8.6×10⁻³	5	0.17	总Ni	2.05×10⁻³	1	0.21
总As	1.66×10⁻³	5	0.03	总As	1.0×10⁻³	0.5	0.20
总Cr	5.6×10⁻³	15	0.04	总Cr	1.83×10⁻³	1.5	0.12
Cr(Ⅵ)	*4×10⁻³	5	0.00	Cr(Ⅵ)	*4×10⁻³	0.5	0.02
总Se	8.0×10⁻⁴	1	0.08	总Se	*4.0×10⁻⁴	0.2	0.00
总Hg	4.0×10⁻⁴	0.1	0.40	总Hg	4.2×10⁻⁴	0.05	0.84
总Be	*7.0×10⁻⁴	0.02	0.00	总Be	*4.0×10⁻⁵	0.005	0.00
总Ag	*2.9×10⁻³	5	0.00	总Ag	8×10⁻⁵	0.5	0.02
F	2.36	100	2.36	F	2.36	100	2.36
总Ba	2.10×10⁻²	100	0.02	总Mn	0.398	2	19.90
pH	8.11	12.5		pH	8.1	6～9
注：“*”表示检测结果低于检出限，数值为该项目方法检出限；F指不包括氟化钙的无机氟化物含量；占比指钛石膏浸出液中危害成分浓度与危险废物标准限值的比值。

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表 3 雨水连续静态浸出安全性试验的变温组浸出毒性

Table 3. Leaching toxicity of variable temperature group in continuous static leaching safety test of rainwater

	测定条件			含量/(μg·L⁻¹)
	温度范围/ ℃	pH	浸出时间/d	Cr	Ni	Cu	Zn	As	Cd	Hg	Pb
测定值	30～45	5	64	1.40	1.36	0.18	2.47	9.45	*0.05	*0.07	*0.09
危险废物鉴别标准限值	30～45	5	64	1.5×10⁴	5×10³	1×10⁵	1×10⁵	5×10³	1×10³	1×10²	5×10³
注：“*”表示检测结果低于检出限，数值为该项目方法检出限。

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表 4 国内各地区关于土壤氟的现存标准及限值

Table 4. Existing standards and limits of soil fluorine in various regions of China

地区	标准名称及编号	指标	最低限值/(mg·kg⁻¹)
北京市	场地土壤环境风险评价筛选值 DB11 /T 811—2011	氟化物	（住宅用地）650
广东省	土壤重金属风险评价筛选值珠江三角洲DB44 /T 1415—2014	氟化物	（居住用地）1000
重庆市	场地土壤环境风险评估筛选值 DB50 /T 723—2016	可溶性氟化物	（居住用地）950
河北省	建设用地土壤污染风险筛选值 DB13 /T 5216—2020	可溶性氟化物	（敏感用地）1950
广东省深圳市	建设用地土壤污染风险筛选值和管制值(DB4403 /T 67—2020)	总氟化物	（第一类用地）1960

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表 5 钛石膏的重金属污染单因子指数和内梅罗指数

Table 5. Single factor index and Nemerow index of heavy metals of titanium gypsum

项目	单因子污染指数（$ {p}_{i} $）
	平均值		变异系数/%		范围
	干样	湿样	干样	湿样	干样	湿样
Cd	1.00	0.52	5.00	5.59	0.95～1.05	0.50～0.55
Hg	0.18	0.13	7.81	7.77	0.17～0.19	0.12～0.14
Pb	0.43	0.10	6.67	15.75	0.40～0.46	0.09～0.11
Cr	1.05	0.55	0.92	7.12	1.04～1.06	0.51～0.59
As	0.59	1.10	1.95	5.19	0.59～0.61	1.05～1.16
Ni	0.84	0.51	1.71	7.51	0.83～0.85	0.48～0.55
Cu	1.00	0.61	0.70	7.16	1.00～1.01	0.57～0.66
Zn	1.70	1.69	2.81	2.64	1.65～1.75	1.64～1.72
$ P_{i\mathrm{\ a}\mathrm{v}\mathrm{e}} $	0.85	0.65	3.45	7.34
$ P_{i\mathrm{\ m}\mathrm{a}\mathrm{x}} $					1.75	1.72
内梅罗指数（$ P $）	1.37	1.30

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表 6 干、湿样钛石膏的土壤特性

Table 6. Soil properties of dry and wet titanium gypsum

试样	pH （酸碱度）	全盐（可溶性盐）/ (g·kg⁻¹)	有机质（总有机碳）/(g·kg⁻¹)	速效氮（碱解氮）/ (mg·kg⁻¹)	速效磷（碱性有效磷）/(mg·kg⁻¹)	速效钾/ (mg·kg⁻¹)	全氮/ (g·kg⁻¹)	全磷/ (g·kg⁻¹)	全钾/ (g·kg⁻¹)
干样钛石膏	±8.14	±17.21	±3.97	±8.00	±0.50	±181.67	±0.23	±0.04	±2.62
湿样钛石膏	±8.36	±17.73	±2.63	±7.00	±0.80	±75.67	±0.23	±0.04	±2.53

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表 7 以土壤含盐量划分的盐渍土类型与植物生长的关系

Table 7. Relationship between saline soil type and plant growth by soil salt content

盐分/(g·kg⁻¹)	盐渍化程度	植物生长状况
<0.1	非盐渍化土壤	对作物不产生盐害
1.0～3.0	盐渍化土	对盐分极敏感的作物产量可能受到影响
3.0～5.0	中度盐土	对盐分敏感作物产量受到影响，但对耐盐作物（苜蓿、棉花、甜菜、高粱、谷子）无多大影响
5.0～10.0	重盐土	只有耐盐作物有收成，但影响种子发芽，而且出现缺苗，严重影响产量
>10.0	极重盐土	只有极少数耐盐植物能生长，如耐盐的牧草、灌木、树木等

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