广西土壤镉含量状况与风险评估研究进展
钟雪梅1a, 夏德尚1b,2,*, 宋波1b,2,*, 陈同斌1b,3,*
1. 桂林理工大学 a. 地球科学学院,b. 环境科学与工程学院,广西 桂林 541004
2. 广西环境污染控制理论与技术重点实验室,广西 桂林 541004
3. 中国科学院地理科学与资源研究所,北京100101
*通信作者简介:宋波(1972- ),男,博士,教授,主要从事区域环境调查与风险评估及污染土壤修复工作。E-mail: songbo@glut.edu.cn

第一作者简介:钟雪梅(1968- ),女,副教授,主要从事区域环境调查与风险评估研究。E-mail: zxm_glite@163.com

摘要

为阐述广西土壤镉含量现状及其潜在风险,论文通过搜集和分析近20 a来公开发表的关于广西区土壤镉含量的文献,共筛选出目标文献60篇,涉及广西30多个地区,样品7 090个,总结了广西区土壤镉含量分布状况与超标情况,以期为相关研究、环境决策和环境管理提供参考。结果表明:广西区土壤镉含量范围、算术均值、几何均值分别为0.040~244.1、12.23、1.884 mg·kg-1,不同功能区的土壤镉含量分布存在较大差异,调查区域中背景土壤镉含量平均值为0.153 mg·kg-1;非矿区农用土壤和城市土壤镉含量的几何均值分别为0.467、0.320 mg·kg-1;工矿区土壤与矿区农用土壤镉含量的几何均值为7.147、6.643 mg·kg-1,分别是背景土壤镉含量平均值的46.71、43.42倍,单项污染指数分别为7.15、6.64;农田土壤大部分维持在中等污染水平,南丹、环江、金城江、大新等县区土壤受矿区污染影响较大。基于搜集到的文献资料及未调查的区域,建议对南丹、金城江、刁江、大环江、阳朔等区域采取治理措施,对百色德保县、平果县、田东县、田阳县等铝矿主产区进行重点调查,以及矿区周边的农用土壤进行重点监测。

关键词: ; 风险评估; 土壤; 广西; 综述
中图分类号:X820.4 文献标志码:A 文章编号:1000-3037(2017)07-1256-15
Review on Soil Cadmium Study and Risk Assessment in Guangxi
ZHONG Xue-mei1a,1, XIA De-shang1a,1, SONG Bo1b,2,*, CHEN Tong-bin1b,3,*
1. a. College of Earth Science, b. College of Environmental Science and Engineering, Guilin University of Technology,Guilin 541004, China
2. Guangxi Key Laboratory of Environmental Pollution Control Theory and Technology, Guilin University of Technology, Guilin 541004, China
3. Institute of Geographic Sciences and Natural Resources Research, CAS, Beijing 100101, China
Abstract

In order to expound the present situation and the potential risk of soil cadmium (Cd) in Guangxi, the paper collected and analyzed literatures about soil Cd in Guangxi which were published in recent 20 years. Based on the uniform criteria, 60 references were selected involving more than 30 areas in Guangxi, 7 090 samples. The paper summarized the distribution of soil Cd content distribution and the situation of soil Cd content exceeding the standard in Guangxi, so as to provide reference for relevant research, environmental policy making and environmental management. Results show that the soil Cd content in Guanxi ranges 0.040-244.1 mg·kg-1, with arithmetic mean and geometric mean 12.23 and 1.884 mg·kg-1, respectively. There were great differences in soil Cd concentration distribution between different functional areas. The average background soil Cd content in the research area is 0.153 mg·kg-1. The geometric mean of Cd content in agricultural soils and urban soils of non-mining areas were 0.467 and 0.320 mg·kg-1, respectively. The geometric mean of Cd content in the soil of mining area and in agricultural soil of mining area were 7.147 and 6.643 mg·kg-1, which were 46.71 and 43.42 times of the background soil Cd content. The majority of farmland soils are maintained at moderate pollution levels. Soils in several counties such as Nandan, Huanjiang, Jinchengjiang and Daxin were greatly affected by the pollution in mining area. There are areas not involved in the collected literatures. We recommend that control measures should be taken in Nandan, Jinchengjiang, Big Huanjiang, Yangshuo and Diaojiang areas, major investigations should be made in Baise Debao, Pingguo, Tiandong and Tianyang aluminum ore producing areas, and monitors on agricultural soil surrounding the mining area should be done.

Keyword: cadmium; risk assessment; soil; Guangxi; review

随着国民经济的发展,土壤重金属污染日趋严峻。自然界中镉常伴生在铅、锌等金属矿石中,这些矿石的开采、冶炼和加工均会引起伴生的镉进入土壤环境中[1]。镉是人体多器官、多系统的毒物,不易经生物降解,其半衰期长(达20~30 a)[2, 3]。世界卫生组织(WHO)和美国环境保护署(USEPA)规定镉的最大允许摄入量均为1 μg·kg-1·d-1 [4]。镉在环境中不会分解,污染排放的镉最终会蓄积在土壤中,几十年长期存在,持续影响农产品安全和人群健康。联合国国际环境规划署和国际劳动卫生重金属委员会把镉列入重点研究的环境污染物[5]

目前,国内外学者对土壤重金属镉做了大量研究,我国北京[6, 7]、湖北[8]、贵州[9]、成都[10]、广东[11]等地及国外的哈塔伊[12]、马德里[13]、那不勒斯[14]、扎姆法拉州[15]等地区均有相关调查。各地区的调查结果具有一定的参考价值,由于信息相对零散及区域差异性等问题,针对我国广西区土壤镉含量分布状况的研究鲜有报道。广西矿产资源丰富,锰矿、锡矿的开采规模与强度居全国之首,是我国典型的喀斯特地貌发育区,同时也是生态脆弱区[16]。广西地处亚热带,水、光、温资源丰富,农作物种类多,复种指数高,是全国重要的双季稻产区,糖料甘蔗、水果、蔬菜等产业位居全国前列[17]。在已有报道中,南丹[18]、环江[19]、西江流域[20]地区矿业活动释放的镉通过土壤及食物链等途径威胁人体健康,其中叶菜类的蔬菜比其他水果蔬菜更易富集镉元素[21],基于公开文献报道资料,本文探讨广西土壤镉含量和空间分布状况并进行风险评估,对进一步开展广西土壤镉含量的调查和治理工作具有一定的参考价值和指导意义。

1 材料与方法
1.1 文献搜集与整理

从公开发表的文献中检索1990年以来关于土壤及部分可食用农产品镉含量的数据。检索依据为:1)以中文关键词“ 土壤” “ 镉(Cd)” “ 重金属” “ 污染” “ 评价” 和英文关键词“ soil” “ cadmium” “ Cd” “ heavy metals” “ pollution” “ assessment” 为关键词在中国知网、万方和Springer、Web of Science(SCI)、Science Direct(Elsevier)等各大数据库检索相关文献。2)在检索到的目标文献中,根据调查区域中不同功能区及背景的差别,将采样点归为5类功能区土壤:即Ⅰ自然土壤,指基本不受人类活动影响的土壤; Ⅱ城区土壤,指城市中心人口密集区的土壤,包括住宅区、公园、商场、医院、学校、各大机构等; Ⅲ工矿区土壤,指矿区周边用于农业生产之外的土壤; Ⅳ矿区农用土壤,指矿区周边用于农业生产的土壤; Ⅴ非矿区农用土壤,指远离工厂的用于农业生产的土壤,包括农田、菜地、茶园、果园、牧场等。3)根据检索到的目标文献,某些文献报道了多种功能区土壤镉含量,因此按土壤功能将该篇文献拆分。4)检索结果用目标文献土壤中镉含量的平均值表示,单位为mg·kg-1。检索到的广西土壤镉样本及样点分布如图1所示,其中样点来源是本课题组在桂林市曾开展的调查工作,共192个土壤样点,包括160个农用土壤样点和32个自然土壤样点,覆盖桂林市全境13个县区。矿产分布情况参照《广西壮族自治区区域地质志》及《中国地壳演化与矿产分布图集》。

图1 广西地区土壤镉样本及样点分布Fig. 1 Sample and sampling sites of soil cadmium in Guangxi

1.2 数据整理与分析

为使数据具有可比性,便于与我国现行的土壤环境质量标准限值进行比较,采用以下几点为依据对数据进行归纳整理:1)文献中对调查区域土壤镉含量作了直接表述的,使用文献中的数据作为该调查区域土壤镉含量(mg·kg-1),本文采用算术均值表示该区域土壤镉含量; 2)文献中没有对调查地区土壤镉含量作直接表述的,通过文献中的图表获得调查地区的土壤镉含量(mg·kg-1); 3)数字和图表都没有的不参与比较和计算。

原始数据处理分析采用SPSS 19.0软件完成,土壤重金属含量的空间分布图用ArcGIS 10.1等软件制作。

1.3 土壤污染评价方法

单因子污染指数法[22]是以土壤元素背景值为评价标准来评价重金属元素的累积污染程度,是国内通用的一种重金属污染评价方法,是国内评价土壤和河流沉积物重金属污染的常用方法。计算公式如下:

P=C/S

式中:< i> P< /i> 为土壤中镉的污染指数; < i> C< /i> 为土壤中镉的实测平均含量(mg·kg-1); < i> S< /i> 为土壤镉的评价标准值(mg·kg-1),不同土壤环境质量执行《土壤环境质量标准》(GB15618—1995)中不同的级别标准值,其中自然土壤执行一级标准(0.20 mg·kg-1),城区土壤、非矿区农用土壤执行二级标准(0.30 mg·kg-1),工矿区土壤及矿区农用土壤执行三级标准(1.0 mg·kg-1)。

分级标准:当< i> P< /i> ≤1时,表示土壤未受污染; 1< < i> P< /i> ≤2时,表示土壤受到轻微污染; 2< < i> P< /i> ≤3时,表示土壤受到轻度污染; 3< < i> P< /i> ≤5时,表示土壤受到中度污染; < i> P< /i> > 5时,表示土壤受到重度污染。< i> P< /i> 值越大表示污染越严重。

2 结果与分析
2.1 广西土壤镉含量特征

根据统计结果显示,广西各地区土壤镉含量存在较大差异,镉含量均值范围为0.04~244.1 mg·kg-1。根据文献中对广西部分地区镉含量的报导情况,统计了广西土壤镉含量状况,为了尊重文献的真实性与可查度,对于样品量大于1的文献,对文献中没有明确给出镉含量变化图表的情况,没有镉含量的变化范围(表1)。在检索到的文献中,根据土壤的采样点位,矿区分布于河池市南丹县、桂林市荔浦县、崇左市大新县、柳州市融安县、柳州市来宾县、桂平市木圭镇、百色市德保县、百色市靖西县等。

表1 广西部分地区土壤镉含量统计 Table 1 The soil cadmium contents in several areas in Guangxi

搜集到广西土壤镉含量的文献量为96(其中存在交叉文献), 各地区土壤镉含量均值呈偏态分布 [pk-s=0.000, 图2(a)], 经对数转换后符合正态分布 [pk-s=0.565, 图2(b)], 其镉含量均值的中值、算术均值、标准差、几何均值和几何标准差分别为1.318 mg· kg-1、12.232 mg· kg-1、31.779 mg· kg-1、1.884 mg· kg-1和7.768。得出广西区土壤镉含量(几何均值)是我国《土壤环境质量标准》(GB15618— 1995)二级标准限制值的6.28倍。河池市金城江区的土壤镉含量最高, 为244.1 mg· kg-1, 单因子污染指数为244.1。

图2 广西部分地区土壤镉含量分布特征Fig. 2 Frequency distribution of cadmium contents in soil in Guangxi

2.2 不同功能区土壤镉含量差异

按照土地利用方式及其所在区域, 将土壤分为自然土壤、工矿区土壤、矿区农用土壤、非工矿区农用土壤和城区土壤5种类型。5种功能区土壤分别对应的文献有4、21、30、37、4篇(其中存在交叉文献), 经Kolmogorov-Smirnov(K-S)正态检验, 自然土壤和城区土壤镉含量符合正态分布, 经对数转换后工矿区土壤、矿区农用土壤和非矿区农用土壤镉含量符合正态分布, 统计结果如表2所示。

表2 不同功能区土壤镉含量状况 Table 2 Soil cadmium content in different land use types

通过几何均值比较, 发现土壤中镉含量水平表现为工矿区土壤> 矿区农用土壤> 非矿区农用土壤> 城区土壤> 自然土壤。自然土壤镉含量的几何均值高于广西土壤镉背景值(0.062 mg· kg-1[26], 较大值出现在桂林市。首先, 这可能与桂林地区喀斯特岩溶地貌特征和土壤背景值(0.119 mg· kg-1)较高有关, 但在《土壤环境质量标准》(GB15618— 1995)一级标准(0.20 mg· kg-1)限值以内; 其次, 桂林地区土壤成土母质主要为第四纪红壤和石灰岩, 其镉含量范围为0.258~2.514和2.542~3.854 mg· kg-1 [24], 明显高于其他地区。非矿区农田土壤与土壤环境质量标准(GB15618— 1995)二级标准(0.30 mg· kg-1)进行比较, 镉含量超标较为严重的是桂林恭城县、桂林市平乐县、南宁市郊区、都安县, 镉平均含量分别为2.01、7.27、1.84、4.11 mg· kg-1。桂林市菜地土壤出现显著的镉累积效应[23], 南宁市蔬菜产地土壤受到不同程度的重金属污染, 以重金属镉最为严重, 可能是菜地复种指数大, 长期施用垃圾肥、污泥、化肥、农药、生长素、工业“ 三废” 排放等[65], 都安耕地土壤镉超标严重, 70.6%的土壤样本超标, 平均超标6.85倍, 达到重度污染水平, 镉是都安县耕地土壤的主要污染元素[60]。百色右江区的水果园与茶区土壤镉含量在安全范围以内。工矿区土壤和矿区农用土壤几何均值与土壤环境质量标准(GB15618— 1995)三级标准(1.0 mg· kg-1)进行比较, 分别是三级标准的7.1和6.6倍, 超标率几乎为100%, 这可能是在矿形成的过程中伴生了镉元素所导致的。南丹大厂矿区农田土壤污染程度最为严重的元素为镉, 污染程度表现出距离矿区及选矿厂越近, 污染有加重趋势, 矿区附近农田土壤不仅重金属污染比较严重, 而且具有较高的生态风险和潜在生态风险, 这些农田已经不适宜生产, 需要进行监控和污染治理[18]。金城江的岩溶区冶炼厂镉主要分布在0~20 cm表层土壤, 其下层污染并不明显, 表明污染来自干湿沉降[45], 阳朔思的村铅锌尾矿砂坝坍塌造成的重金属污染农田中, 玉米地、柑橘园和水稻田中, 镉超标最为严重[56]

从变异系数的角度来看, 变异系数≤ 10%时, 表现为弱变异性; 变异系数介于10%~100%之间表现为中等变异性; 变异系数≥ 100%时表现为强变异性。在5种功能区土壤中, 自然土壤和城区土壤镉含量的空间变异性表现为中等强度; 工矿区土壤、矿区农用土壤和非矿区农用土壤镉含量空间变异性强。全部土壤的变异系数为259.8%, 为强变异性, 说明土壤镉含量受矿业冶炼和人为活动的影响很大。

根据搜集到的广西土壤样本镉含量的文献资料, 运用ArcGIS 10.1绘制广西区土壤镉含量的空间分布图(图3), 其中:图3(a)为文献中镉含量的平均值, 包括本课题组在桂林市13个县曾开展的调查样点; 图3(b)为文献中高镉含量, 指目标文献中样本镉含量范围的最大值。

图3 广西各地区土壤样本镉均值(a)和最高值(b)空间分布Fig. 3 Spatial distribution of the average value (a) and the highest value (b) of sampled soil cadmium content in Guangxi

通过调查区域土壤镉含量均值与高值分布图, 可以看出大部分地区的镉含量在1.0~50 mg· kg-1范围内, 根据土壤质量环境标准(GB15618— 1995)三级标准限值为1.0 mg· kg-1, 表明大部分地区的镉含量存在超标现象, 河池地区镉含量超标现象尤为突出, 这与河池地区矿区开采、冶炼有很大关系。其中通过图3(b)的高值分布图可以看出, 最高值也在河池市南丹县, 这与其他研究该地区的数据相符。同时桂林农田土壤镉含量超标率达到85.5%[23], 通过收集到的文献显示矿区与农田超标主要集中在河池市、百色市、南宁市、桂林市。

3 讨论

根据广西矿区资料绘出广西矿产分布图, 广西地区金属矿种主要有金、铝、锰、铅锌、锑、铁、钨、锡矿(图4)。

图4 广西矿区与样本镉含量分布Fig. 4 Distribution of cadmium mining area and cadmium content in Guangxi

广西耕地土壤类型以红壤和赤红壤为主, 耕地土壤有机质含量平均为3.19%, 全氮含量平均为0.18%, 速效磷含量平均为19.59 mg· kg-1, 土壤pH值范围为4.30~8.54, 平均值为6.20, 偏酸性[17]。其中农药和化肥的使用会影响土壤肥力, 据统计, 2000— 2008年, 广西地区农药使用量由39 806 t增加到54 622 t; 化肥施用量由157.76× 104t增加到222.58× 104t, 农药、化肥的大量使用是造成土壤重金属积累的主要途径[17, 76], 因此, 广西耕地土壤肥力失衡和重金属镉超标率较高, 极有可能与农药、化肥的大量使用有关。

广西素有“ 有色金属之乡” 的美誉, 锡多金属成矿带内蕴藏着非常丰富的金属矿产资源。累计探明金属储量:锡116.3× 104t, 锌471.5× 104t, 铅107.5× 104t, 锑91.8× 104t, 镉2.09× 104t[78]。根据图4及表1, 研究主要集中在河池南丹矿区、大环江沿岸、金城江区、百色市、都安县、桂林各县市、南宁市城郊, 其中河池、百色地区遭受了不同程度的镉污染问题, 这与该地区矿业活动有密切关系, 河池市有色金属矿区主要分布在南丹县, 以锡多金属矿种为主, 该区矿区土壤和农田土壤的数据显示, 该区镉含量存在严重超标现象, 用单项污染指数评价该区具有高危风险。百色市有色金属矿主要分布在德保县、平果县、田东县、田阳县等地, 以铝矿、锡矿为主, 对该区的矿区和农田土壤研究表明, 该区镉含量普遍超标, 目前对该区的矿区和农田土壤研究较少, 而且该区是铝矿的主产区, 建议对该区重点调查。在长期的矿业开采过程中, 大量的尾矿库被废弃, 通过表面侵蚀、风化、排水作用, 矿山废弃物污染了地势较低的耕地[79], 金属矿山冶炼、尾矿库、化石燃料燃烧与污水排放是镉污染的主要来源[80, 81]。龙江河镉污染事件, 就是由于采矿和冶炼, 通过废水、废气、废渣直接排放到地下溶洞, 造成龙江河上中游镉污染严重, 下游柳江段未出现河水镉含量超标情况[82, 83]。镉元素进入人体会使人体骨骼疏松, 如痛痛病[84]。由矿山冶炼与尾矿库对土壤、水体、沉积物造成镉危害已迫在眉睫, 需引起足够的重视。

4 结论与展望

根据上述统计数据及对数据进行各指标评价得出:1)广西区土壤镉含量范围、算术均值、几何均值分别为0.040~244.1、12.232、1.884 mg· kg-1, 不同类型土壤镉含量水平表现为工矿区土壤(7.147 mg· kg-1)> 矿区农用土壤(6.643 mg· kg-1)> 非矿区农用土壤(0.467 mg· kg-1)> 城区土壤(0.320 mg· kg-1)> 自然土壤(0.153 mg· kg-1); 2)工矿区土壤、矿区农用土壤镉含量普遍偏高, 单项污染指数分别为7.15、6.64; 3)农田土壤大部分维持在中等污染水平, 南丹、环江、金城江、大新等县区流域土壤受矿区污染影响较大。

广西为“ 有色金属” 之乡, 矿区范围大, 对农田土壤有很大影响, 建议对矿区周边农田土壤重点调查, 尤其是百色市矿区多, 而研究土壤重金属含量的文章较少。

The authors have declared that no competing interests exist.

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