Article(id=1209819474342056027, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1209811339510411616, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2404157, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1717430400000, receivedDateStr=2024-06-04, revisedDate=1736179200000, revisedDateStr=2025-01-07, acceptedDate=null, acceptedDateStr=null, onlineDate=1766373040042, onlineDateStr=2025-12-22, pubDate=1751904000000, pubDateStr=2025-07-08, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766373040042, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766373040042, creator=13701087609, updateTime=1766373040042, updator=13701087609, issue=Issue{id=1209811339510411616, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='19', pageStart='7885', pageEnd='8315', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766371100547, creator=13701087609, updateTime=1766373228996, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1209820266960654935, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1209811339510411616, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1209820266960654936, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1209811339510411616, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=8297, endPage=8306, ext={EN=ArticleExt(id=1209819475927502975, articleId=1209819474342056027, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=Characteristics and Risk Assessment of Heavy Metal Contents in Calcium-containing Biological Minerals, columnId=1209819472542699530, journalTitle=Science Technology and Engineering, columnName=Papers∙Environmental and Safe Science, runingTitle=null, highlight=null, articleAbstract=

To investigate the contents and pollution of heavy metals in calcium-containing biological minerals, 16 samples were collected from three primary categories: eggshells, shells, and animal bones. Inductively coupled plasma optical emission spectrometry (ICP-OES) was utilized to analyze the contents of seven metalloids and heavy metals (As, Cd, Pb, Cr, Cu, Zn, and Mn). The pollution degree and risk of heavy metals were evaluated using single-factor, Nemerow comprehensive pollution index method, Hakanson potential ecological risk index method, and health risk comprehensive assessment. The results show that As and Cd are not detected in all calcium-containing biological minerals, meanwhile Pb is not detected in both eggshells and shells. Five heavy metals (Pb, Cr, Cu, Zn, and Mn) are detected in the remaining samples, with their contents remaining below standard. Differences in heavy metal contents are observed among different categories and species. Cu, Mn, and Zn have the highest contents of 14.85, 21.47, and 201.99 mg/kg, respectively accumulated in eggshells, shells, and animal bones. The risk assessment results show that the single-factor pollution index of four heavy metals (Pb, Cr, Cu, Zn) in calcium-containing biological minerals is less than 1.0 and the comprehensive pollution index is less than 0.7. All samples are indicated as unpolluted. The potential ecological risk among three types of calcium-containing biological minerals is in descending order: animal bones > eggshells > shells. The non-carcinogenic total risk index of two exposure pathways for minors and adults is less than the safety threshold of 1.0. This finding indicates that five heavy metals in calcium-containing biological minerals are unlikely to threaten human health. Overall, calcium-containing biological minerals can be used as potential sources of fertilizers and soil conditioners in agricultural production. However, their usage should be controlled to prevent heavy metal accumulation and pollution.

, correspAuthors=Xue-qin TAO, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Hui-shi CHEN, Xiong-kai ZHENG, Jia-yu WANG, Ai-ping JIA, Meng-yao ZOU, Xue-qin TAO, Jian-jun DU), CN=ArticleExt(id=1209819477424869599, articleId=1209819474342056027, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=钙基生物矿物中重金属含量特征及风险评价, columnId=1209819472702083086, journalTitle=科学技术与工程, columnName=论文∙环境科学、安全科学, runingTitle=null, highlight=null, articleAbstract=为了解钙基生物矿物中重金属的含量及污染情况,采集了16种涵盖蛋壳、贝壳、畜骨3种主要类别的样品,采用电感耦合等离子体发射光谱法(inductively coupled plasma optical emission spectrometry, ICP-OES)测定7种重(类)金属(As、Cd、Pb、Cr、Cu、Zn、Mn)的含量,并采用单因子、内梅罗综合污染指数法、Hakanson潜在生态风险指数法和健康风险综合评价其重金属污染程度与风险。结果表明:所有钙基生物矿物中As、Cd均未检出,蛋壳类、贝壳类中Pb未检出,其余均检测出5种重金属(Pb、Cr、Cu、Zn、Mn),且重金属含量均未超标。不同类别不同种之间重金属含量有所差异,其中Cu、Mn、Zn含量最高分别为14.85、21.47、201.99 mg/kg,分别积累在蛋壳、贝壳、畜骨中。风险评价结果表明,钙基生物矿物中4种重金属(Pb、Cr、Cu、Zn)的单因子污染指数均小于1.0,综合污染指数均小于0.7,所有样品处于未污染水平。3类钙基生物矿物中潜在生态风险排序依次为畜骨类>蛋壳类>贝壳类。未成年人和成年人两种暴露途径的非致癌总风险指数均小于安全阈值1.0,表明钙基生物矿物中5种重金属基本不会对人体造成健康危害。总体而言,钙基生物矿物可作为农业生产过程中的潜在肥料及土壤调理剂来源,但应控制其使用量,防止重金属累积污染。, correspAuthors=陶雪琴, authorNote=null, correspAuthorsNote=
*陶雪琴(1978—),女,汉族,湖南邵阳人,博士,教授。研究方向:环境修复技术与农业资源利用。E-mail:
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=9A5C21QWOtWtLNzUs/g9/A==, magXml=+G7uD/BDnRWBp/kKZ/FwZA==, pdfUrl=null, pdf=EaZxEiT8dBe7ymrI2bGERQ==, pdfFileSize=4905261, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=XP8v+yPvLabtinw8Tt/4nw==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=NfZ7kKLyZBVruLLwsA4etQ==, mapNumber=null, authorCompany=null, fund=null, authors=

陈惠诗(1999—),女,汉族,广东茂名人,硕士研究生。研究方向:农业资源利用。E-mail:

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陈惠诗(1999—),女,汉族,广东茂名人,硕士研究生。研究方向:农业资源利用。E-mail:

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陈惠诗(1999—),女,汉族,广东茂名人,硕士研究生。研究方向:农业资源利用。E-mail:

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Biological Trace Element Research, 2018, 184(2): 501-507., articleTitle=Health risk contamination of heavy metals in yolk and albumen of duck eggs collected in central and western Thailand, refAbstract=null), Reference(id=1209885652448048064, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, doi=null, pmid=null, pmcid=null, year=2024, volume=41, issue=2, pageStart=442, pageEnd=451, url=null, language=null, rfNumber=[45], rfOrder=59, authorNames=王家裕, 何振贤, 郑雄开, journalName=农业资源与环境学报, refType=null, unstructuredReference=王家裕, 何振贤, 郑雄开, 等. 鸽粪农业利用潜力及其重金属风险评价[J]. 农业资源与环境学报, 2024, 41(2): 442-451., articleTitle=鸽粪农业利用潜力及其重金属风险评价, refAbstract=null), Reference(id=1209885652510962625, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, doi=null, pmid=null, pmcid=null, year=2024, volume=41, issue=2, pageStart=442, pageEnd=451, url=null, language=null, rfNumber=[45], rfOrder=60, authorNames=Wang Jiayu, He Zhenxian, Zheng Xiongkai, journalName=Journal of Agricultural Resources and Environment, refType=null, unstructuredReference=Wang Jiayu, He Zhenxian, Zheng Xiongkai, et al. 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Pure and Applied Biology, 2015, 4(2): 187-194., articleTitle=Response of cauliflower (Brassica oleracea L. botrytis) cultivars to phosphorus levels, refAbstract=null), Reference(id=1209885652620014531, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, doi=null, pmid=null, pmcid=null, year=2021, volume=11, issue=11, pageStart=2210, pageEnd=null, url=null, language=null, rfNumber=[47], rfOrder=62, authorNames=Mohamed M H M, Ali M, Eid R S M, journalName=Agronomy, refType=null, unstructuredReference=Mohamed M H M, Ali M, Eid R S M, et al. Phosphorus and biofertilizer application effects on growth parameters, yield and chemical constituents of Broccoli[J]. Agronomy, 2021, 11(11): 2210., articleTitle=Phosphorus and biofertilizer application effects on growth parameters, yield and chemical constituents of Broccoli, refAbstract=null)], funds=[Fund(id=1209885647813341991, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, awardId=2020B0202080002, language=CN, fundingSource=广东省重点领域研发计划(2020B0202080002), fundOrder=null, country=null), Fund(id=1209885647880450856, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, awardId=2019B110207001, language=CN, fundingSource=广东省重点领域研发计划(2019B110207001), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1209885642050368065, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, xref=1, ext=[AuthorCompanyExt(id=1209885642071339587, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, companyId=1209885642050368065, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 Guangdong Provincial Engineering and Technology Research Center for Agricultural and Pollution Prevention and Control, School of Resources and Environmental, Zhongkai University of Agriculture and Engineering, Guangzhou 510225, China), AuthorCompanyExt(id=1209885642083922500, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, companyId=1209885642050368065, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 仲恺农业工程学院资源与环境学院, 广东省农业产地环境污染防控工程技术研究中心, 广州 510225)]), AuthorCompany(id=1209885642172002890, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, xref=2, ext=[AuthorCompanyExt(id=1209885642197168715, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, companyId=1209885642172002890, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 School of Environment and Energy, South China University of Technology, Guangzhou 510006, China), AuthorCompanyExt(id=1209885642209751628, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, companyId=1209885642172002890, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 华南理工大学环境与能源学院, 广州 510006)])], figs=[ArticleFig(id=1209885645540029155, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Fig.1, caption=Distribution situation of heavy metal contents in different species of calcium-containing biological minerals, figureFileSmall=vZPF8JgOTtFqAJJGlxwGDg==, figureFileBig=R21NOMkXLbLLO0GtXAU8GQ==, tableContent=null), ArticleFig(id=1209885645628109542, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=图1, caption=不同类别钙基生物矿物中重金属含量分布情况, figureFileSmall=vZPF8JgOTtFqAJJGlxwGDg==, figureFileBig=R21NOMkXLbLLO0GtXAU8GQ==, tableContent=null), ArticleFig(id=1209885645783298795, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Fig.2, caption=Heavy metal contents in calcium-containing biological minerals, figureFileSmall=c/fGq2ROGN9y1qQID/32sw==, figureFileBig=0XDsBQkRppWwH1dc/KgHQw==, tableContent=null), ArticleFig(id=1209885645867184878, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=图2, caption=钙基生物矿物中重金属含量

不同字母表示不同钙基生物矿物有显著差异(p﹤0.05)

, figureFileSmall=c/fGq2ROGN9y1qQID/32sw==, figureFileBig=0XDsBQkRppWwH1dc/KgHQw==, tableContent=null), ArticleFig(id=1209885645955265264, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Fig.3, caption=Single-factor pollution index and composite pollution index of heavy metals in calcium-containing biological minerals, figureFileSmall=Kun5zYO8fSWNph82cqNbJA==, figureFileBig=AGJ0whnuNsvdi4/e9mpKlA==, tableContent=null), ArticleFig(id=1209885646047539956, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=图3, caption=钙基生物矿物中重金属单因子污染指数和综合污染指数, figureFileSmall=Kun5zYO8fSWNph82cqNbJA==, figureFileBig=AGJ0whnuNsvdi4/e9mpKlA==, tableContent=null), ArticleFig(id=1209885646114648820, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Fig.4, caption=Single-factor pollution index and composite pollution index in different species of calcium-containing biological minerals, figureFileSmall=D3F62gYR3NAj0nFMPcJvpQ==, figureFileBig=u7UrtkOas7dmG+3FsVmgDQ==, tableContent=null), ArticleFig(id=1209885646282420983, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=图4, caption=不同类别钙基生物矿物中重金属单因子污染指数和综合污染指数, figureFileSmall=D3F62gYR3NAj0nFMPcJvpQ==, figureFileBig=u7UrtkOas7dmG+3FsVmgDQ==, tableContent=null), ArticleFig(id=1209885646374695673, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Fig.5, caption=Eecological risk factor and the potential ecological risk index of heavy metals in different species of calcium-containing biological minerals, figureFileSmall=NvpuV9v21u78Bw57LaA/Rg==, figureFileBig=V/o6NFZ3WQ3asMPdPE0UWQ==, tableContent=null), ArticleFig(id=1209885646450193147, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=图5, caption=不同类别钙基生物矿物中各重金属生态风险系数和潜在生态风险指数, figureFileSmall=NvpuV9v21u78Bw57LaA/Rg==, figureFileBig=V/o6NFZ3WQ3asMPdPE0UWQ==, tableContent=null), ArticleFig(id=1209885646538273530, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Fig.6, caption=Non-carcinogenic risk for minors and adults, figureFileSmall=q53tA7sj4BIWiwDweVcaQQ==, figureFileBig=7QEHebGDqY6Gah6NKtV6wg==, tableContent=null), ArticleFig(id=1209885646643131135, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=图6, caption=未成年人和成年人的非致癌风险, figureFileSmall=q53tA7sj4BIWiwDweVcaQQ==, figureFileBig=7QEHebGDqY6Gah6NKtV6wg==, tableContent=null), ArticleFig(id=1209885646760571650, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Table 1, caption=

Evaluation standards of heavy metal pollutants in calcium-containing biological minerals

, figureFileSmall=null, figureFileBig=null, tableContent=
参考标准 浓度/(mg·kg-1)
As Cd Pb Cr Cu Zn Mn
《土壤调理剂及使用规程餐厨废物原料》(NY/T 3935—2021) 5 5 25 25
德国腐熟肥料标准 100 400
中国土壤元素背景值 11.2 0.097 26 61 22.6 74.2 583
), ArticleFig(id=1209885646836069126, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=表1, caption=

钙基生物矿物中重金属污染物评价标准

, figureFileSmall=null, figureFileBig=null, tableContent=
参考标准 浓度/(mg·kg-1)
As Cd Pb Cr Cu Zn Mn
《土壤调理剂及使用规程餐厨废物原料》(NY/T 3935—2021) 5 5 25 25
德国腐熟肥料标准 100 400
中国土壤元素背景值 11.2 0.097 26 61 22.6 74.2 583
), ArticleFig(id=1209885646915760904, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Table 2, caption=

Grade standards for single factor and Nemero comprehensive pollution index

, figureFileSmall=null, figureFileBig=null, tableContent=
等级 单因子污染指数法 综合污染指数法
单因子污染指数(Pi) 污染程度 综合污染指数(Pz) 污染程度
1 Pi≤1 未污染 Pz≤0.7 安全
2 1<Pi≤2 轻度污染 0.7<Pz≤1 警戒线
3 2<Pi≤3 中度污染 1<Pz≤2 轻度污染
4 Pi>3 重度污染 2<Pz≤3 中度污染
5 Pz>3 重度污染
), ArticleFig(id=1209885647003841292, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=表2, caption=

单因子和内梅罗综合污染指数分级标准

, figureFileSmall=null, figureFileBig=null, tableContent=
等级 单因子污染指数法 综合污染指数法
单因子污染指数(Pi) 污染程度 综合污染指数(Pz) 污染程度
1 Pi≤1 未污染 Pz≤0.7 安全
2 1<Pi≤2 轻度污染 0.7<Pz≤1 警戒线
3 2<Pi≤3 中度污染 1<Pz≤2 轻度污染
4 Pi>3 重度污染 2<Pz≤3 中度污染
5 Pz>3 重度污染
), ArticleFig(id=1209885647083533069, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Table 3, caption=

Grade standards for Hakanson potential ecological risk index

, figureFileSmall=null, figureFileBig=null, tableContent=
等级 Hakanson潜在生态风险指数法
生态风险系数( E i r) 生态风险程度 潜在生态风险指数(RI) 生态风险程度
1 E i r<40 轻微 RI<150 轻微
2 40≤ E i r<80 中等 150≤RI<300 中等
3 80≤ E i r<160 较强 300≤RI<600
4 160≤ E i r<320 RI≥600 极强
5 E i r≥320 极强
), ArticleFig(id=1209885647188390674, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=表3, caption=

Hakanson潜在生态风险指数分级标准

, figureFileSmall=null, figureFileBig=null, tableContent=
等级 Hakanson潜在生态风险指数法
生态风险系数( E i r) 生态风险程度 潜在生态风险指数(RI) 生态风险程度
1 E i r<40 轻微 RI<150 轻微
2 40≤ E i r<80 中等 150≤RI<300 中等
3 80≤ E i r<160 较强 300≤RI<600
4 160≤ E i r<320 RI≥600 极强
5 E i r≥320 极强
), ArticleFig(id=1209885647268082452, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Table 4, caption=

Health risk assessment values of heavy metals in calcium-containing biological minerals

, figureFileSmall=null, figureFileBig=null, tableContent=
参数 定义 成年人取值 未成年人取值 文献
cs 重金属元素含量/(mg·kg-1) 本研究
EF 暴露频率/(d·a-1) 350 350 [25]
ED 暴露持续时间/a 20 6
BW 体质量/kg 70 20
AT 平均暴露时间/d ED×365(非致癌)
70×365(致癌)
IRing 钙基生物矿物的摄入率/(mg·d-1) 100 200
SA 暴露的皮肤表面积/cm2 5 700 2 800
SAF 皮肤的黏附因子/(mg·cm-2) 0.07 0.2
ABS[26] 皮肤的吸收因子 0.001
), ArticleFig(id=1209885647347774231, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=表4, caption=

钙基生物矿物重金属元素健康风险评估参数值

, figureFileSmall=null, figureFileBig=null, tableContent=
参数 定义 成年人取值 未成年人取值 文献
cs 重金属元素含量/(mg·kg-1) 本研究
EF 暴露频率/(d·a-1) 350 350 [25]
ED 暴露持续时间/a 20 6
BW 体质量/kg 70 20
AT 平均暴露时间/d ED×365(非致癌)
70×365(致癌)
IRing 钙基生物矿物的摄入率/(mg·d-1) 100 200
SA 暴露的皮肤表面积/cm2 5 700 2 800
SAF 皮肤的黏附因子/(mg·cm-2) 0.07 0.2
ABS[26] 皮肤的吸收因子 0.001
), ArticleFig(id=1209885647427466011, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Table 5, caption=

Reference dose (RfD) for each heavy metals in carcinogenic risk

, figureFileSmall=null, figureFileBig=null, tableContent=
暴露途径 参数 Pb Cr Cu Zn Mn
经口摄入 RfD 3.50×10-3 3.00×10-3 4.00×10-2 3.00×10-1 1.4×10-1
SF
皮肤接触 RfD 5.25×10-4 6.00×10-5 1.20×10-2 6.00×10-2 3.00×10-4
SF
), ArticleFig(id=1209885647486186269, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=表5, caption=

致癌风险中不同重金属参考剂量(RfD)

, figureFileSmall=null, figureFileBig=null, tableContent=
暴露途径 参数 Pb Cr Cu Zn Mn
经口摄入 RfD 3.50×10-3 3.00×10-3 4.00×10-2 3.00×10-1 1.4×10-1
SF
皮肤接触 RfD 5.25×10-4 6.00×10-5 1.20×10-2 6.00×10-2 3.00×10-4
SF
), ArticleFig(id=1209885647561683745, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=EN, label=Table 6, caption=

Statistics of heavy metal contents in different species of calcium-containing biological minerals

, figureFileSmall=null, figureFileBig=null, tableContent=
类别 元素 最大值/
(mg·kg-1)
最小值/
(mg·kg-1)
中位值/
(mg·kg-1)
平均值/
(mg·kg-1)
标准差/
(mg·kg-1)
变异系数/% 标准值/
(mg·kg-1)
蛋壳类 Pb ≤25
Cr 2.82 1.50 1.83 2.03 0.54 26.8 ≤25
Cu 14.85 1.77 2.06 4.56 5.76 126.2 ≤100
Zn 3.88 3.28 3.50 3.56 0.28 7.9 ≤400
Mn 0.85 0.38 0.53 0.59 0.18 30.4
贝壳类 Pb ≤25
Cr 10.90 4.88 7.89 7.89 4.26 54.0 ≤25
Cu 2.45 2.00 2.23 2.23 0.32 14.2 ≤100
Zn 6.65 6.38 6.52 6.52 0.19 2.8 ≤400
Mn 21.17 17.98 19.57 19.57 2.26 11.5 -
畜骨类 Pb 3.64 1.26 2.13 2.37 0.77 32.6 ≤25
Cr 17.73 2.96 7.38 8.55 5.00 58.5 ≤25
Cu 4.85 2.05 2.19 2.73 0.95 34.9 ≤100
Zn 201.99 76.85 112.93 123.84 43.20 34.9 ≤400
Mn 11.32 1.74 2.33 3.73 3.06 82.1
), ArticleFig(id=1209885647641375523, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1209819474342056027, language=CN, label=表6, caption=

不同类别钙基生物矿物中重金属含量统计

, figureFileSmall=null, figureFileBig=null, tableContent=
类别 元素 最大值/
(mg·kg-1)
最小值/
(mg·kg-1)
中位值/
(mg·kg-1)
平均值/
(mg·kg-1)
标准差/
(mg·kg-1)
变异系数/% 标准值/
(mg·kg-1)
蛋壳类 Pb ≤25
Cr 2.82 1.50 1.83 2.03 0.54 26.8 ≤25
Cu 14.85 1.77 2.06 4.56 5.76 126.2 ≤100
Zn 3.88 3.28 3.50 3.56 0.28 7.9 ≤400
Mn 0.85 0.38 0.53 0.59 0.18 30.4
贝壳类 Pb ≤25
Cr 10.90 4.88 7.89 7.89 4.26 54.0 ≤25
Cu 2.45 2.00 2.23 2.23 0.32 14.2 ≤100
Zn 6.65 6.38 6.52 6.52 0.19 2.8 ≤400
Mn 21.17 17.98 19.57 19.57 2.26 11.5 -
畜骨类 Pb 3.64 1.26 2.13 2.37 0.77 32.6 ≤25
Cr 17.73 2.96 7.38 8.55 5.00 58.5 ≤25
Cu 4.85 2.05 2.19 2.73 0.95 34.9 ≤100
Zn 201.99 76.85 112.93 123.84 43.20 34.9 ≤400
Mn 11.32 1.74 2.33 3.73 3.06 82.1
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钙基生物矿物中重金属含量特征及风险评价
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陈惠诗 1 , 郑雄开 2 , 王家裕 1 , 贾爱萍 1 , 邹梦遥 1 , 陶雪琴 1, * , 杜建军 1
科学技术与工程 | 论文∙环境科学、安全科学 2025,25(19): 8297-8306
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科学技术与工程 | 论文∙环境科学、安全科学 2025, 25(19): 8297-8306
钙基生物矿物中重金属含量特征及风险评价
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陈惠诗1 , 郑雄开2, 王家裕1, 贾爱萍1, 邹梦遥1, 陶雪琴1, * , 杜建军1
作者信息
  • 1 仲恺农业工程学院资源与环境学院, 广东省农业产地环境污染防控工程技术研究中心, 广州 510225
  • 2 华南理工大学环境与能源学院, 广州 510006
  • 陈惠诗(1999—),女,汉族,广东茂名人,硕士研究生。研究方向:农业资源利用。E-mail:

通讯作者:

*陶雪琴(1978—),女,汉族,湖南邵阳人,博士,教授。研究方向:环境修复技术与农业资源利用。E-mail:
Characteristics and Risk Assessment of Heavy Metal Contents in Calcium-containing Biological Minerals
Hui-shi CHEN1 , Xiong-kai ZHENG2, Jia-yu WANG1, Ai-ping JIA1, Meng-yao ZOU1, Xue-qin TAO1, * , Jian-jun DU1
Affiliations
  • 1 Guangdong Provincial Engineering and Technology Research Center for Agricultural and Pollution Prevention and Control, School of Resources and Environmental, Zhongkai University of Agriculture and Engineering, Guangzhou 510225, China
  • 2 School of Environment and Energy, South China University of Technology, Guangzhou 510006, China
出版时间: 2025-07-08 doi: 10.12404/j.issn.1671-1815.2404157
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为了解钙基生物矿物中重金属的含量及污染情况,采集了16种涵盖蛋壳、贝壳、畜骨3种主要类别的样品,采用电感耦合等离子体发射光谱法(inductively coupled plasma optical emission spectrometry, ICP-OES)测定7种重(类)金属(As、Cd、Pb、Cr、Cu、Zn、Mn)的含量,并采用单因子、内梅罗综合污染指数法、Hakanson潜在生态风险指数法和健康风险综合评价其重金属污染程度与风险。结果表明:所有钙基生物矿物中As、Cd均未检出,蛋壳类、贝壳类中Pb未检出,其余均检测出5种重金属(Pb、Cr、Cu、Zn、Mn),且重金属含量均未超标。不同类别不同种之间重金属含量有所差异,其中Cu、Mn、Zn含量最高分别为14.85、21.47、201.99 mg/kg,分别积累在蛋壳、贝壳、畜骨中。风险评价结果表明,钙基生物矿物中4种重金属(Pb、Cr、Cu、Zn)的单因子污染指数均小于1.0,综合污染指数均小于0.7,所有样品处于未污染水平。3类钙基生物矿物中潜在生态风险排序依次为畜骨类>蛋壳类>贝壳类。未成年人和成年人两种暴露途径的非致癌总风险指数均小于安全阈值1.0,表明钙基生物矿物中5种重金属基本不会对人体造成健康危害。总体而言,钙基生物矿物可作为农业生产过程中的潜在肥料及土壤调理剂来源,但应控制其使用量,防止重金属累积污染。
钙基生物矿物  /  重金属  /  污染评价  /  健康风险

To investigate the contents and pollution of heavy metals in calcium-containing biological minerals, 16 samples were collected from three primary categories: eggshells, shells, and animal bones. Inductively coupled plasma optical emission spectrometry (ICP-OES) was utilized to analyze the contents of seven metalloids and heavy metals (As, Cd, Pb, Cr, Cu, Zn, and Mn). The pollution degree and risk of heavy metals were evaluated using single-factor, Nemerow comprehensive pollution index method, Hakanson potential ecological risk index method, and health risk comprehensive assessment. The results show that As and Cd are not detected in all calcium-containing biological minerals, meanwhile Pb is not detected in both eggshells and shells. Five heavy metals (Pb, Cr, Cu, Zn, and Mn) are detected in the remaining samples, with their contents remaining below standard. Differences in heavy metal contents are observed among different categories and species. Cu, Mn, and Zn have the highest contents of 14.85, 21.47, and 201.99 mg/kg, respectively accumulated in eggshells, shells, and animal bones. The risk assessment results show that the single-factor pollution index of four heavy metals (Pb, Cr, Cu, Zn) in calcium-containing biological minerals is less than 1.0 and the comprehensive pollution index is less than 0.7. All samples are indicated as unpolluted. The potential ecological risk among three types of calcium-containing biological minerals is in descending order: animal bones > eggshells > shells. The non-carcinogenic total risk index of two exposure pathways for minors and adults is less than the safety threshold of 1.0. This finding indicates that five heavy metals in calcium-containing biological minerals are unlikely to threaten human health. Overall, calcium-containing biological minerals can be used as potential sources of fertilizers and soil conditioners in agricultural production. However, their usage should be controlled to prevent heavy metal accumulation and pollution.

calcium-containing biological minerals  /  heavy metals  /  pollution assessment  /  health risk
陈惠诗, 郑雄开, 王家裕, 贾爱萍, 邹梦遥, 陶雪琴, 杜建军. 钙基生物矿物中重金属含量特征及风险评价. 科学技术与工程, 2025 , 25 (19) : 8297 -8306 . DOI: 10.12404/j.issn.1671-1815.2404157
Hui-shi CHEN, Xiong-kai ZHENG, Jia-yu WANG, Ai-ping JIA, Meng-yao ZOU, Xue-qin TAO, Jian-jun DU. Characteristics and Risk Assessment of Heavy Metal Contents in Calcium-containing Biological Minerals[J]. Science Technology and Engineering, 2025 , 25 (19) : 8297 -8306 . DOI: 10.12404/j.issn.1671-1815.2404157
根据《中国统计年鉴2023》[1]公布的数据显示,2022年中国禽蛋、海水贝类、肉类的总产量分别为3 456.4、1 605.9、9 328.4万t。按蛋壳、贝壳、畜骨分别占蛋类、海水贝类、家畜体总质量的10%、60%、20%计算,每年将产生近350万t的蛋壳、960万t的贝壳以及1 865万t的畜骨。这些肉类、蛋类、海水产品的消费增长导致了相关农业废弃物(蛋壳、贝壳、畜骨)的增加,未经处理的这些废弃物容易发生腐败变质,滋生蚊蝇并产生有毒物质和有害气体,直接或间接地对生态环境造成严重的污染[2]。因此,如何将蛋壳、贝壳、畜骨变废为宝,提升社会和经济效益,实现资源再利用化成为目前的研究热点。
有研究提出鸡蛋壳和骨粉不仅是农业废弃物,还是钙基生物矿物[3]。钙基生物矿物是指由生物过程直接或间接控制合成的以钙为主要元素的有机-无机杂糅矿物[4]。这些矿物通常在生物结构中发挥着重要的作用,例如作为坚固的支撑材料参与生物体的运动过程或作为外壳保护软组织[5]。钙基生物矿物根据其无机组成可被划分碳酸钙型和磷酸钙型两大类。碳酸钙型(如方解石、文石和球霰石)生物矿物主要是由碳酸钙以不同的晶体形态沉积形成[6],这类矿物不仅构成了大量海洋生物(如贝类、甲壳类动物、以及硬骨珊瑚等)的外壳或骨骼[7],在一些植物与昆虫的结构中也普遍存在[8]。它们在形态和性质上各不相同,有的以纯净的矿物形态存在,而有的则与有机物质杂糅[9],在微观尺度上形成复杂的组织结构。磷酸钙型(包括羟基磷灰石、磷酸八钙和无定形磷酸钙)是以磷酸钙为主的一类生物矿物,以钙磷灰石的形式存在于脊椎动物的骨骼和牙齿中[10]。这类矿物质能够为骨骼提供必要的硬度和耐用性,并且在骨骼的生长、修复以及钙离子储存与释放等生物功能中发挥着关键作用[11-13]。针对这些特点,可将钙基生物矿物作为土壤改良剂、调理剂等用于农业和环境治理领域。蛋壳粉、畜骨粉符合《土壤调理剂及使用规程 餐厨废物原料》(NY/T 3935—2021)[14]的农业标准,将其制备成土壤调理剂施用于土壤中,可有效改善土壤酸化,钝化重金属活性,从而达到调酸、补钙,蓄肥缓释、修复土壤的效果,还可促进作物对土壤养分的吸收,提高作物产量,改善作物品质,降低土壤中重金属的生物可利用性与植物中重金属的含量[15]。Zheng等[16]研究表明,牡蛎壳粉和畜骨粉的施用增加了土壤的pH、某些养分的含量以及过氧化氢酶和脲酶的活性,同时降低了Cd、Pb、Cu和Zn的生物可利用性。Muyassir等[17]研究发现,鸡蛋壳粉作为土壤增强剂含有宏观和微量营养素,可增加芥菜的生长和产量。
综上所述,前人的研究已经证明蛋壳、贝壳、畜骨等钙基生物矿物可以作为改良剂、调理剂,在重金属污染土壤修复治理中广泛应用,但是贝类水产、畜禽在养殖过程中,会通过养殖饲料、养殖环境等途径富集重金属,导致以此为原料生产的土壤调理剂重金属元素超标[18]。孙蓟锋等[19]研究发现,以牡蛎壳、磷矿石等为原材料的矿物源土壤调理剂中存在As、Pb、Cr 3种重金属元素超过限量规定的情况,尤其Pb元素导致的不合格率达20.9%。然而,针对钙基生物矿物自身重金属含量及潜在的污染风险尚未充分研究。鉴于此,本研究对16种涵盖蛋壳类、贝壳类、畜骨类的钙基生物矿物进行As、Cd、Pb、Cr、Cu、Zn、Mn 7种元素含量的测定,旨在分析及评估其重金属含量累积特征和污染程度,了解其安全风险,以期为中国农业生产、土壤污染治理等过程中钙基生物矿物作为肥料、土壤调理剂的选择应用提供依据和保障。
从广东、广西、四川、浙江、江苏、山东、河北、河南等8个省(自治区)收集共16种钙基生物矿物材料,其中蛋壳类5种(土鸡蛋蛋壳、白凤乌鸡蛋蛋壳、七彩野山鸡蛋蛋壳、鸭蛋壳、鹅蛋壳)、贝壳类两种(牡蛎壳、扇贝壳)、畜骨类9种(三黄鸡鸡骨、清远鸡鸡骨、乌鸡鸡骨、鸭骨、黄牛骨、水牛骨、牦牛骨、山羊骨、猪骨)。所有样品经沸水滚煮2 h,除去血水、油脂及表面杂质,后用超纯水反复冲洗,放置105 ℃烘箱中烘至恒重。研磨粉碎后,过100目尼龙筛,保存备用。
样品中Cr、Cd、Cu、Zn、Pb、Mn总量的消解方法:称取0.500 0 g(精确到0.000 1 g)样品于消解管中,加入9 mL盐酸、3 mL硝酸。加盖于180 ℃加热60 min,后开盖180 ℃赶酸至1~2 mL,继续加王水重复上述步骤进行消解至澄清透明。后赶酸至不流动的液珠状,加3 mL硝酸,180 ℃赶酸至1~2 mL。待冷却至室温后润洗全量转移,超纯水定容,混匀备用。
样品中As总量的消解方法:称取0.500 0 g(精确到0.000 1 g)样品于消解管中,加入9 mL盐酸、3 mL硝酸,加盖于100 ℃加热150 min。待冷却至室温后润洗全量转移,超纯水定容,混匀备用。
采用电感耦合等离子体发射光谱仪(Avio 550Max)测定钙基生物矿物中Cr、Cd、Cu、Zn、Pb、Mn及As的含量。同时,样品空白和国家标准物质(石灰岩,GBW 07120)按照上述方法进行消解和重金属含量测定,国家标准物质消解液中重金属含量的标准值和实测值相对偏差均小于10%。所用水为超纯水,所用试剂均为分析纯。
各样品均设置3组平行,取平均值作为检测结果,并采用SPSS和Origin对钙基生物矿物样品重金属含量进行统计分析和作图。
(1)单因子污染指数法。采用单因子污染指数法[20]对钙基生物矿物中的单个重金属元素的污染程度进行评价。其计算公式为
P i = C i S i
式(1)中:Pi为重金属 i的单因子污染指数;Ci为重金属 i的平均浓度,mg/kg;Si为重金属i相应的限量标准值,mg/kg。重金属污染评价标准值如表1所示,采用《土壤调理剂及使用规程 餐厨废物原料》(NY/T 3935—2021)[14]进行评价。由于该标准中不包含Cu、Zn污染限量,Cu、Zn的评价标准按德国腐熟堆肥标准[21]。Mn无限量标准。
(2)内梅罗综合污染指数法。采用内梅罗综合污染指数法[20]是在单因子污染指数法的基础上,综合评价钙基生物矿物中重金属总体污染程度。其计算公式为
P z = ( C i / S i ) m a x 2 + ( C i / S i ) a v g 2 2
式(2)中:Pz为内梅罗综合污染指数;(Ci/Si)max为重金属i的单因子污染指数的最大值,mg/kg;(Ci/Si)avg为重金属i的单因子污染指数的平均值,mg/kg。单因子和内梅罗综合污染指数分级标准如表2所示。
(3)Hakanson潜在生态风险指数法。采用Hakanson潜在生态风险指数法[22],对钙基生物矿物中重金属污染的潜在生态风险进行评价。其计算公式为
E r i = T r i C f i = T r i C d i C r i
R I = i = 1 n E r i
式中:RI为多种重金属元素的综合潜在生态风险指数; E i r为重金属i的生态风险系数; T i r为重金属元素i的毒性相应系数,不同重金属元素毒性响应系数[23]为Zn=Mn=1,Pb=Cu=5,Cr=2; C i f为重金属i的污染系数; C i d为钙基生物矿物重金属元素i 的实测含量,mg/kg; C i r为土壤中重金属i的参照值,mg/kg。本文中采用中国土壤元素背景值[24]作为土壤中重金属元素的参照值,如表1所示。Hakanson潜在生态风险指数分级标准如表3所示。
采用美国环保署(U.S. Environmental Protection Agency,USEPA)推荐的健康风险评价模型作为健康风险评价方法,评估和分析钙基生物矿物带来的健康风险[25-26]。经口摄入和皮肤接触是钙基生物矿物重金属元素的主要暴露途径,因此,本文中仅评估经口摄入和皮肤接触两种暴露途径。模型计算公式为
A D I i n g = c s × I R i n g × E F × E D B W × A T × 10 - 6
A D I d e r m a l = c s × S A × S A F × A B S × E F × E D B W × A T × 10 - 6
式中:ADIing和ADIdermal分别为经口摄入和皮肤接触吸收的日平均剂量,mg/(kg·d);cs为钙基生物矿物中某种重金属元素的含量;IRing为钙基生物矿物的摄入率;EF为暴露频率;ED为暴露持续时间;SA为暴露的皮肤表面积;SAF为皮肤的黏附因子;ABS为皮肤的吸收因子;BW为体质量;AT为平均暴露时间,相关参数值如表4所示。
健康风险评价模型中将化学物质分为非致癌物质与致癌物质2类,分别进行非致癌风险和致癌风险计算。多种重金属元素总的非致癌风险指数用HI表示,当HI<1时,非致癌风险较小或可忽略;当HI≥1时,则存在非致癌风险。多种重金属总的致癌风险指数用TCR表示,当TCR<10-6时,表示无明显的致癌风险;当10-6≤TCR<10-4时,表示可能存在致癌风险;当TCR≥10-4时,则表示存在显著的致癌风险。
非致癌风险计算公式为
H I = H Q i = A D I i j R f D i j
致癌风险计算公式为
T C R = C R i j = A D I i j × S F i j
式中:i为重金属元素的数量;j为经口摄入、皮肤接触两种暴露途径;RfD为不同暴露途径下每种重金属元素的参考剂量,mg/(kg·d);SF为不同暴露途径下每种重金属元素的斜率因子,mg/(kg·d);HQ为单种重金属元素在不同途径下的非致癌风险的危害指数;CR为单种重金属元素在两种暴露途径下总的致癌风险指数,相关参数值如表5所示。
试验分别测定了16种钙基生物矿物中的Cr、Cd、Cu、Zn、Pb、Mn及As的含量。结果显示,除Cd、As元素和蛋壳类、贝壳类材料中的Pb元素低于仪器检出限外,其他重金属均被检出。3类钙基生物矿物中重金属含量统计如表6所示,其中Cr、Pb、Cu、Zn含量均低于中国土壤调理剂重金属标准(NY/T 3935—2021)和德国腐熟粪肥标准限值。整体上看,重金属的含量排序为:畜骨类>贝壳类>蛋壳类。不同类别的钙基生物矿物中重金属含量的分布情况如图1所示,蛋壳类中Cu>Zn>Cr>Mn>Pb,贝壳类中Mn>Cr>Zn>Cu>Pb,畜骨类中Zn>Cr>Mn>Cu>Pb。
钙基生物矿物中重金属含量如图2所示。不同类别不同种之间的同种重金属含量存在差异。对比发现,蛋壳类中Cr、Pb含量较低且组间无明显差异,而畜骨类中Cr、Pb富集量较高且不同种间的富集水平不一致,其中黄牛骨、牦牛骨的Cr、Pb含量最高,Cr含量分别为17.73、15.96 mg/kg,Pb含量分别为3.64、3.04 mg/kg 。按照《土壤调理剂及使用规程 餐厨废物原料》(NY/T 3935—2021)农业标准,钙基生物矿物中Cr、Pb含量均在安全范围内。此外,各种钙基生物矿物中Cu含量基本在1.77~4.85 mg/kg,仅蛋壳类中鸭蛋壳Cu含量最高,为14.85 mg/kg,且明显高于其他种3~8倍。相比之下,钙基生物矿物中Zn含量在不同类别不同种之间差异最为显著,畜骨类的Zn含量均在76.85~201.99 mg/kg,明显高于另外两类的23~61倍,畜骨类中鸭骨的Zn含量最高,为201.99 mg/kg 。按照德国腐熟肥料标准,钙基生物矿物中Cu、Zn均为超标。此外,与其他种相比,牡蛎壳、扇贝壳的Mn含量最高,分别为17.98、21.47 mg/kg 。
采用单因子污染指数和综合污染指数法分别评价不同重金属元素在各种钙基生物矿物中的污染程度,及其总体重金属污染状况,结果如图3所示。16种钙基生物矿物中Cr的Pi最高,其中,黄牛骨最高为0.71,其次为Zn、Cu、Pb,所有样品中重金属Pi均小于1.0,处于未污染水平。16种钙基生物矿物中重金属Pz均小于0.7,处于安全水平。不同类别钙基生物矿物中重金属单因子污染指数和综合污染指数如图4所示,蛋壳类和贝壳类重金属单因子污染指数从大到小顺序依次为Cr>Cu>Zn>Pb,畜骨类为Cr>Zn>Pb>Cu,在3类钙基生物矿物中重金属综合污染指数从大到小顺序依次为畜骨类>贝壳类>蛋壳类。
钙基生物矿物广泛存在于自然环境中,且人为收集加工后可以作为功能材料施入土壤中,采用Hakanson潜在生态风险指数法评价其重金属污染的潜在生态风险,结果如图5所示。5种重金属潜在生态危害影响顺序依次为Zn>Cu>Pb>Cr>Mn,且重金属潜在生态风险系数( E i r)均小于40,潜在危害程度低。3类钙基生物矿物中潜在生态风险顺序依次为畜骨类>蛋壳类>贝壳类,且总体潜在生态风险指数(RI)均小于150,重金属总体潜在生态风险属低程度范围。
钙基生物矿物作为人类餐饮常见的物质,其内含的重金属易通过口食进入人体,因此有必要对其进行健康风险评价。由于会引起致癌风险的As、Cd均未检出,本研究仅分析评价钙基生物矿物中Pb、Mn、Cu、Zn、Cr 5种重金属引起的非致癌风险。钙基生物矿物中两种不同暴露途径和不同重金属元素的非致癌风险如图6所示,5种重金属在两种暴露途径下未成年人和成年人的非致癌风险(HI)顺序为Cr>Pb>Zn>Mn>Cu,且均呈未成年人高于成年人的特征。未成年人和成年人两种暴露途径的非致癌总风险分别为0.50、0.08,均小于安全阈值1.0,表明钙基生物矿物不会对人体健康产生风险危害。
为探究钙基生物矿物中重金属含量和污染情况,本研究对蛋壳类、贝壳类、畜骨类等16种钙基生物矿物进行了重金属含量分析,并采用单因子、内梅罗综合污染指数法、潜在生态风险进行重金属污染风险评价及健康风险评价。本研究结果表明,所有钙基生物矿物中均未检出As、Cd,与Barwisch等[27]的研究相似,其分析了德国东北部的鹤类蛋壳中的As、Cd、Cu和Pb的浓度,蛋壳样品中仅发现Cu和Pb,且这两种金属的含量都没有超过被认为对鸟类具有潜在毒性的浓度;Mukhtar等[28]研究了各种重金属在两种鸟类的各器官中的积累水平,发现骨骼中As和Cd是积累最少的重金属。
钙基生物矿物中普遍含有Pb、Cr、Cu、Zn、Mn等重金属元素,且在不同类别和不同种之间的重金属含量分布存在差异。在蛋壳类中,各种重金属元素的含量较低,仅鸭蛋壳中Cu、Mn含量最高,分别为14.85、0.80 mg/kg,显著高于鸡蛋壳和鹅蛋壳。该结果与Voica等[29]、张亚男等[30]的研究相似,鸡蛋壳中Cu、Mn含量较低,分别为0.233~1.808 mg/kg 和ND(未检出)~1.772 mg/kg ;而与鸡蛋相比,鸭蛋壳Ca和Zn含量无显著差异,但鸭蛋壳的P、Cu和Mn的含量显著升高。这可能与蛋鸭饲粮中的Cu、Mn水平均高于蛋鸡饲粮有关。Mn、Zn和Cu等是蛋壳形成过程的必需微量元素,因此,饲粮添加Cu、Mn等微量元素可促进其在蛋壳内的沉积,而调控蛋壳品质[31]。除了分析家禽类蛋壳中的重金属含量,夏秋烨等[32]、Mora[33]、Rani等[34]还研究了白鹭蛋壳中的重金属残留情况,其结果表明,不同地区的白鹭蛋壳中重金属浓度有显著差异,小白鹭蛋壳中含量较高的重金属元素为Zn、Cu。结合本文研究结果说明,不管是家禽类还是飞禽类,其蛋壳中主要积累的重金属元素相同,为Zn、Cu。
在贝壳类中,Mn的含量最高,在17.97~21.17 mg/kg,与张敏等[35]研究结果相似,贝壳中Cu、Fe、Zn元素含量较低,但Mn元素含量超过平均水平,且Mn含量高于其他种。贝壳中重金属积累与水体或底泥中重金属的含量密切相关,通常水体或底泥中重金属含量越高,生物体积累的重金属含量越高[36]。宋德宏等[37]的研究发现,牡蛎壳体可以替代贝类的软组织作为监测海域环境的载体,指示海域环境重金属的变化情况,例如双壳类动物能够大量累积有机污染物,Cu能够与有机污染物结合,通过牡蛎壳体及软组织吸收富集在壳体上,因此贝壳类生物对水体中重金属的积累反映了环境污染程度。本研究中,贝壳类中5种重金属含量按大到小顺序依次为Mn(19.57 mg/kg)>Cr(7.89 mg/kg)>Zn(6.52 mg/kg)>Cu(2.23 mg/kg)>Pb(ND),与Nour等[38]的研究相比,贝壳中重金属含量均偏低。
在畜骨类中,Zn的含量最高,在76.85~201.99 mg/kg,远远大于其他金属元素,这可能与动物骨骼生长和骨化过程中Zn的重要性有关[39]。研究表明Zn对动物骨骼的形成和发育起着关键作用,缺乏Zn可能导致动物骨骼受损[40]。同时,骨骼是Zn主要储存器官,当动物体内Zn供应过量或缺乏时,其能够储存和动员Zn[41]。而Cu在动物骨骼中的含量较低,本文研究中畜骨类中的Cu含量平均值为2.73 mg/kg,与Zetzsche等[42]、Blavi等[43]的研究相似,猪体内Cu含量较低,且当Cu供应过量时,主要储存在肝脏中而非骨骼中。与蛋壳类、贝壳类相比,畜骨类中的Cr含量最高,为8.55 mg/kg,而Cr作为微量矿物元素,可以提高畜禽的生长性能,改善胴体品质[44],因此养殖场为了促进畜禽快速生长,提高肉类品质,在饲料中添加Cr,导致畜骨中Cr含量增加。由于畜禽养殖场养殖的畜禽不同,饲料添加情况不同,也会导致鸡、猪、牛等畜禽种中Cr含量不同。因此,应从畜禽饲料、饲料添加剂以及养殖环境中等源头控制禽蛋、贝类、畜禽的重金属富集程度,降低其污染及危害风险。
本研究表明,钙基生物矿物的重金属污染与健康风险等级均处于安全水平。为了验证钙基生物矿物农用安全性,根据农田的安全农用年限计算公式[45],结合西兰花一年四作的种植体系,对钙基生物矿物的安全利用年限进行估算(西兰花生长发育受磷肥的高度影响)[46-47],发现钙基生物矿物中Pb、Cr、Cu、Zn的输入对土壤的安全农用年限影响较小可忽略,最低安全农用年限为592年。孙蓟锋等[19]通过分析土壤调理剂所用的原材料发现,中国土壤调理剂产品中重金属元素情况总体处于相对安全的水平范围内,但是矿物源土壤调理剂中As、Pb、Cr元素存在一定质量问题,尤其是Pb元素,而导致其超标所用原料主要包括牡蛎壳、钾长石、磷矿石+碱渣等。牡蛎壳等贝类产品在人工养殖的过程中会富集海水中的Pb、Cr等重金属,且贝壳自身含有的少量重金属元素很难在生产中消除,长期施用可能导致土壤发生重金属污染[18]。本研究结果表明,收集的蛋壳类、贝壳类材料中Pb均未检出,畜骨类材料中Pb、Cr、Cu、Zn、Mn等重金属含量均未超过中国土壤调理剂重金属标准(NY/T 3935—2021)和德国腐熟粪肥标准限值,且总体潜在生态风险很小。因此,利用蛋壳类、贝壳类、畜骨类钙基生物矿物作为原料生产土壤调理剂,能够推进农业资源再利用,符合绿色环保的要求。
(1)本研究所采集的16种钙基生物矿物样品中均含有Pb、Cr、Cu、Zn、Mn等重金属元素,不同类别不同种钙基生物矿物之间的重金属含量分布存在一定的差异,蛋壳类的重金属含量从大到小顺序为Cu>Zn>Cr>Mn>Pb,贝壳类为Mn>Cr>Zn>Cu>Pb,畜骨类为Zn>Cr>Mn>Cu>Pb。同时,重金属Cr、Pb、Cu、Zn含量均在中国土壤调理剂重金属标准(NY/T 3935—2021)、德国腐熟粪肥标准限值内。
(2)16种钙基生物矿物中重金属Pb、Cr、Cu、Zn的单因子污染指数和综合污染指数显示重金属均处于未污染水平。钙基生物矿物重金属综合污染指数从大到小排序为:畜骨类>贝壳类>蛋壳类。钙基生物矿物总体潜在生态风险指数(RI)平均为2.156,小于150,属低风险程度范围,潜在生态风险顺序依次为畜骨类>蛋壳类>贝壳类。
(3)16种钙基生物矿物中重金属在经口摄入、皮肤接触两种暴露途径下,未成年人和成年人的非致癌风险(HI)顺序为Cr>Pb>Zn>Mn>Cu。HI均小于安全阈值1.0,表明钙基生物矿物对人体健康的危害程度可忽略。
  • 广东省重点领域研发计划(2020B0202080002)
  • 广东省重点领域研发计划(2019B110207001)
参考文献 引证文献
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2025年第25卷第19期
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doi: 10.12404/j.issn.1671-1815.2404157
  • 接收时间:2024-06-04
  • 首发时间:2025-12-22
  • 出版时间:2025-07-08
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  • 收稿日期:2024-06-04
  • 修回日期:2025-01-07
基金
广东省重点领域研发计划(2020B0202080002)
广东省重点领域研发计划(2019B110207001)
作者信息
    1 仲恺农业工程学院资源与环境学院, 广东省农业产地环境污染防控工程技术研究中心, 广州 510225
    2 华南理工大学环境与能源学院, 广州 510006

通讯作者:

*陶雪琴(1978—),女,汉族,湖南邵阳人,博士,教授。研究方向:环境修复技术与农业资源利用。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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