Article(id=1153433746884780894, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433737141412332, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20250103005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1735833600000, receivedDateStr=2025-01-03, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1752929635019, onlineDateStr=2025-07-19, pubDate=1745510400000, pubDateStr=2025-04-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752929635019, onlineIssueDateStr=2025-07-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752929635019, creator=13701087609, updateTime=1752929635019, updator=13701087609, issue=Issue{id=1153433737141412332, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='8', pageStart='1', pageEnd='316', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752929632696, creator=13701087609, updateTime=1757293087150, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1171735391666225233, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433737141412332, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1171735391666225234, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1153433737141412332, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=199, endPage=205, ext={EN=ArticleExt(id=1153433747572646778, articleId=1153433746884780894, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Research progress on determination methods for metasilicic acid, columnId=1151895321388347923, journalTitle=Journal of Food Safety & Quality, columnName=Food Analysis and Detection, runingTitle=null, highlight=null, articleAbstract=

Silicon is an essential trace element for the human body and generally exists in mineral water in the form of metasilicic acid. The accurate detection of metasilicic acid, a crucial boundary indicator for natural mineral water, is essential for determining compliance within quality standards. The GB 8538—2022 China national food safety standardTesting methods for natural mineral drinking water specifies 2 kinds of spectrophotometric techniques, the silicomolybdic yellow method and the silicomolybdic blue method, for the detection of metasilicic acid. However, due to factors such as the stability of colorimetric solutions in spectroscopic analysis and differences in absorption wavelengths, the application of these 2 kinds of methods in metasilicic acid detection still presents issues that require further improvement. Researchers have also reported a number of determination methods for metasilicic acid based on different technologies, such as flow injection (FI), inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), ion chromatography (IC), high performance liquid chromatography (HPLC). This article compared the advantages and existing problems of these methods, so as to provide references for the improvement of existing methods and the development of new methods for metasilicic acid determination.

, correspAuthors=Guo-You HOU, 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=Shuai WEI, Nan-Nan SUN, Ying-Ying GAO, Guo-You HOU), CN=ArticleExt(id=1153433753742467188, articleId=1153433746884780894, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=偏硅酸检测方法研究进展, columnId=1151895321958773274, journalTitle=食品安全质量检测学报, columnName=食品分析与检测, runingTitle=null, highlight=null, articleAbstract=

硅是对人体有益的重要微量元素, 一般以偏硅酸的形态存于水中。偏硅酸是天然矿泉水的重要界限指标, 其检测的准确性关系到天然矿泉水品质的合格判定。GB 8538—2022《食品安全国家标准 饮用天然矿泉水检验方法》中规定了硅钼黄和硅钼蓝两种基于分光光度技术的偏硅酸检测方法, 受光谱分析比色液稳定性、吸收波长差异等因素的影响, 这两种方法在偏硅酸检测中的应用仍存在需要改进提升的问题。除国家标准规定的检测方法外, 一些学者也报道了基于流动注射(flow injection, FI)、电感耦合等离子发射光谱(inductively coupled plasma optical emission spectrometry, ICP-OES)、电感耦合等离子体质谱(inductively coupled plasma mass spectrometry, ICP-MS)、离子色谱(ion chromatography, IC)、高效液相色谱(high performance liquid chromatography, HPLC)等技术的偏硅酸检测方法。本文对比分析了多种检测方法的优缺点和检测操作中存在的问题, 为偏硅酸检测方法的改进和新方法的开发提供参考。

, correspAuthors=侯国友, authorNote=null, correspAuthorsNote=
* 侯国友(1968—), 男, 硕士, 高级工程师, 主要研究方向为食品安全。E-mail:
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魏帅(1984—), 男, 博士, 主要研究方向为食品安全。E-mail:

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魏帅(1984—), 男, 博士, 主要研究方向为食品安全。E-mail:

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偏硅酸检测方法研究进展
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魏帅 , 孙南南 , 高英英 , 侯国友 *
食品安全质量检测学报 | 食品分析与检测 2025,16(8): 199-205
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食品安全质量检测学报 | 食品分析与检测 2025, 16(8): 199-205
偏硅酸检测方法研究进展
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魏帅 , 孙南南, 高英英, 侯国友*
作者信息
  • 今麦郎食品股份有限公司食品安全管理中心, 邢台 055350
  • 魏帅(1984—), 男, 博士, 主要研究方向为食品安全。E-mail:

通讯作者:

* 侯国友(1968—), 男, 硕士, 高级工程师, 主要研究方向为食品安全。E-mail:
Research progress on determination methods for metasilicic acid
Shuai WEI , Nan-Nan SUN, Ying-Ying GAO, Guo-You HOU*
Affiliations
  • Food Safety Management Centre, Jinmailang Foods Co., Ltd., Xingtai 055350, China
出版时间: 2025-04-25 doi: 10.19812/j.cnki.jfsq11-5956/ts.20250103005
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硅是对人体有益的重要微量元素, 一般以偏硅酸的形态存于水中。偏硅酸是天然矿泉水的重要界限指标, 其检测的准确性关系到天然矿泉水品质的合格判定。GB 8538—2022《食品安全国家标准 饮用天然矿泉水检验方法》中规定了硅钼黄和硅钼蓝两种基于分光光度技术的偏硅酸检测方法, 受光谱分析比色液稳定性、吸收波长差异等因素的影响, 这两种方法在偏硅酸检测中的应用仍存在需要改进提升的问题。除国家标准规定的检测方法外, 一些学者也报道了基于流动注射(flow injection, FI)、电感耦合等离子发射光谱(inductively coupled plasma optical emission spectrometry, ICP-OES)、电感耦合等离子体质谱(inductively coupled plasma mass spectrometry, ICP-MS)、离子色谱(ion chromatography, IC)、高效液相色谱(high performance liquid chromatography, HPLC)等技术的偏硅酸检测方法。本文对比分析了多种检测方法的优缺点和检测操作中存在的问题, 为偏硅酸检测方法的改进和新方法的开发提供参考。

偏硅酸  /  饮用水  /  检测方法

Silicon is an essential trace element for the human body and generally exists in mineral water in the form of metasilicic acid. The accurate detection of metasilicic acid, a crucial boundary indicator for natural mineral water, is essential for determining compliance within quality standards. The GB 8538—2022 China national food safety standardTesting methods for natural mineral drinking water specifies 2 kinds of spectrophotometric techniques, the silicomolybdic yellow method and the silicomolybdic blue method, for the detection of metasilicic acid. However, due to factors such as the stability of colorimetric solutions in spectroscopic analysis and differences in absorption wavelengths, the application of these 2 kinds of methods in metasilicic acid detection still presents issues that require further improvement. Researchers have also reported a number of determination methods for metasilicic acid based on different technologies, such as flow injection (FI), inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), ion chromatography (IC), high performance liquid chromatography (HPLC). This article compared the advantages and existing problems of these methods, so as to provide references for the improvement of existing methods and the development of new methods for metasilicic acid determination.

metasilicic acid  /  drinking water  /  determination methods
魏帅, 孙南南, 高英英, 侯国友. 偏硅酸检测方法研究进展. 食品安全质量检测学报, 2025 , 16 (8) : 199 -205 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250103005
Shuai WEI, Nan-Nan SUN, Ying-Ying GAO, Guo-You HOU. Research progress on determination methods for metasilicic acid[J]. Journal of Food Safety & Quality, 2025 , 16 (8) : 199 -205 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20250103005
硅是人体不可或缺的元素, 在保证血管渗透性, 增强血管弹力纤维强度, 防止粥样硬化斑块的形成等方面发挥重要作用[1]。硅在水中溶解度很低, 通常以偏硅酸的形式存在[2]。由于偏硅酸是人体内可溶性硅的主要来源, 偏硅酸含量成为评价天然矿泉水品质最常用、最重要的界限指标之一。GB 8537—2018《食品安全国家标准 饮用天然矿泉水》中规定, 偏硅酸型饮用天然矿泉水的偏硅酸含量需大于等于25 mg/L。
为了规范水中偏硅酸含量的测定, GB 8538—2022《食品安全国家标准 饮用天然矿泉水检验方法》中规定了2种偏硅酸的检测方法, 分别是硅钼黄光谱法和硅钼蓝光谱法。随着消费者对偏硅酸关注程度的增高和检测技术的发展, 国内外学者报道了多种适用于水中偏硅酸含量的检测方法, 包括比色法、流动注射分析法(flow injection analysis, FIA)、色谱法、电感耦合等离子体-发射光谱法(inductively coupled plasma optical emission spectrometry/atomic emission spectrometry, ICP-OES/AES)、毛细管电泳-非接触式电导法等多种方法开始应用于偏硅酸的检测工作中。本文总结归纳了国内外偏硅酸含量的测定方法, 旨在为偏硅酸检测方法的提升提供参考。
偏硅酸的化学式为H2SiO3, 天然矿泉水中的偏硅酸主要来自于岩石中的二氧化硅溶解, 有学者认为偏硅酸实际上是二氧化硅的水溶状态, 化学式也可写为(SiO2·H2O)[3-4]。纯净的偏硅酸一般呈现为白色无定形粉末状, 在水溶液中, 呈透明的胶体溶液状。偏硅酸在水中的溶解度很小, 其溶解度受温度影响, 在室温条件下, 偏硅酸在水中的饱和溶解度约为145 mg/kg[5]
偏硅酸对矿泉水口感有正向的作用, 原因是偏硅酸分子能够在水分子之间起到一种类似“润滑剂”的作用, 当水在口腔中流动时, 偏硅酸分子会减少水分子之间以及水与口腔黏膜之间的摩擦力, 让水在口腔中的感觉更加柔和、顺滑。侯明韬等[6]收集了不同品牌的矿泉水与来自中国各省份的自来水, 测试钙、镁、铝、铁、锌、锶、偏硅酸等因素对饮用水口感的影响。结果表明, 偏硅酸的存在有助于改善饮用水的品质, 含有偏硅酸的饮用水呈微甘甜口感。偏硅酸除了可以有效改善矿泉水的口感, 其对人体健康也有明显的促进作用[7]。硅是人体必需的微量元素之一, 偏硅酸作为可溶性硅, 能够通过消化道进入血液循环, 并分布到全身各组织。偏硅酸的主要作用包括: 改善皮肤粗糙[8], 通过促进胶原蛋白和弹性蛋白的生成, 增强皮肤的弹性和保湿能力, 延缓皮肤衰老; 降低动脉硬化的风险[9], 偏硅酸通过促进血管壁中弹性蛋白和胶原蛋白的合成, 增强血管内膜弹力层的弹力纤维强度, 维持血管的弹性和完整性; 预防骨质疏松症[10], 偏硅酸能够与钙、磷等矿物质结合, 促进骨基质的矿化过程, 从而增加骨密度, 避免骨质疏松; 预防老年痴呆症(阿尔茨海默症)[11], β-淀粉样蛋白(amyloid-β protein, Aβ)的异常沉积是老年痴呆症的主要病因, 硅元素能够调节β-分泌酶和γ-分泌酶的活性, 减少Aβ前体蛋白(amyloid precursor protein, APP)的异常切割, 从而降低Aβ的生成, 减少老年痴呆症的发病概率; 降低血糖水平[12], 硅能够促进胰岛素受体底物(insulin receptor substrate, IRS)的磷酸化, 增强胰岛素信号通路的传导, 提高细胞对葡萄糖的摄取和利用, 从而起到降低血糖的作用。
国内外对水中偏硅酸含量的检测方法并不多, 公开文献报道的测试方法包括分光光度法[13-21]、FIA[22-29]、ICP-OES/AES[30-36]、电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry, ICP-MS)[37-38]、离子色谱法[39-42]、毛细管电泳-非接触式电导法[43]、间断化学分析法[44]和快速检测试剂盒[45-46]等。
GB 8538—2022中规定了两种测定矿泉水中偏硅酸的方法, 分别是硅钼黄分光光度法和硅钼蓝分光光度法。硅钼黄法的测定原理是, 在酸性溶液中可溶性硅酸与钼酸铵反应, 生成可溶性的黄色硅钼杂多酸络合物[H4Si(Mo3O10)4], 通过测定黄色硅钼杂多酸在420~430 nm的吸光度, 计算样品中偏硅酸含量。硅钼蓝法则是在硅钼黄法的基础上, ‌加入1,2,4-氨基萘酚磺酸将黄色硅钼杂多酸还原成硅钼蓝, ‌通过测定680 nm的吸光度来计算偏硅酸的浓度。对比两种分光光度法的检测灵敏度可以看出, 硅钼黄法的定量限为1 mg/L, 而硅钼蓝法的灵敏度更高, 定量限为0.1 mg/L。但是由于硅钼蓝法相较于硅钼黄法多了一步还原显色反应, ‌操作步骤增多, ‌操作时间也相对较长。
硅钼黄法是GB 8538—2022规定的第一法, 在实际操作中应用最多, 但部分学者也报道了硅钼黄法测定中存在的问题。袁春晖等[13]研究发现, 在采用硅钼黄法检测矿泉水中偏硅酸含量时, 矿泉水中亚铁离子会在425 nm和470 nm处产生特征吸收峰, 与GB 8538—2022规定的硅钼黄的测定波长420~430 nm存在干扰, 低至4 μg/mL的亚铁离子就可以对偏硅酸的测定结果造成影响。王珏纯[14]通过试验发现硅钼黄法在实际操作过程中存在比色液不稳定的缺陷, 比色液在室温环境静置10、20、30 min后, 检测结果会分别降低4.8%、9.4%、14.4%, 原因是显色的黄色硅钼杂多酸络合物在室温条件下不稳定, 随静置时间增加, 络合物分解, 黄色逐步变淡。
相比于硅钼黄法, 硅钼蓝法被报道的问题主要集中在最大吸收波长的选择上。GB 8538—2022中规定, 硅钼蓝的检测波长为680 nm, 但不同学者对硅钼蓝的检测波长有着不同的观点。陈秋娟等[15]研究发现, 用紫外-可见分光光度计在波长600~900 nm之间扫描, 随着波长的增大, 硅钼蓝的吸光度也随着增大, 硅钼蓝在波长814 nm时吸光度最大。屈瑶[16]测定了不同波长条件下硅钼蓝显色溶液的吸光度, 证明硅钼蓝溶液在810~820 nm波长范围内具有较大的吸光度值, 并选择815 nm作为特征吸光值。侯屹婷[17]报道, 硅钼蓝最大吸收波长是810 nm, 但在640~680 nm处吸光度较为稳定, 建议优选650 nm为最佳吸收波长。李莉莉等[18]测定了硅钼蓝在670~840 nm的吸光值, 结果证明810 nm波长吸光值最高且稳定, 建议选择810 nm作为检测波长。孙楠等[19]的试验也获得类似的研究结果, 其通过光谱扫描方法确认硅钼蓝的最大吸收波长在810 nm附近, 并建议采用810 nm作为分析波长。
一些学者通过试验对GB 8538—2022中并行的两种检测方法的精密度和灵敏度进行了比较。宋连君[20]通过试验比较了硅钼黄法和硅钼蓝法的检测灵敏度, 研究发现硅钼蓝法灵敏度更高, 定量限低至0.1 mg/L, 而同等条件下, 硅钼黄法定量限仅为1 mg/L, 这个结果与GB 8538—2022标注的定量限一致。路润峰等[21]对两种检测方法检测灵敏度的研究结论与前人类似, 同样发现硅钼蓝检出限较低, 为0.02 mg/L, 硅钼黄法的检出限为0.18 mg/L, 推荐在试样含量较低时优选硅钼蓝法。
总的看来, 硅钼黄和硅钼蓝两种方法是现行应用最广泛的偏硅酸分析方法, 也是GB 8538—2022采纳的方法。近年来, 越来越多的学者研究发现, 受光谱分析比色液稳定性、吸收波长差异等因素的影响, 硅钼黄法和硅钼蓝法在偏硅酸检测中的应用仍存在修改提升的空间, 特别是硅钼黄法, 其存在灵敏度不高, 稳定性较差的缺陷, 在实际应用中要重点关注比色液的静置时长对结果的影响。
FIA是1975年由丹麦学者RUZICKA和HANSEN在“流动注射分析”论文中首次提出的[22], 其原理与分光光度法类似, 是通过将一定体积的试样注入到一个流动着的、非空气间隔的硅钼黄或硅钼蓝显色溶液的载流中, 被注入的试样溶液与载流中的试剂在反应盘中混合、反应, 最后进入到检测器进行测定分析及记录的方法(图1)。
李忠波等[23]最早报道了采用流动注射技术测定工业用水中硅的方法, 方法选取了780 nm为吸收波长, 优化设计了流速、反应管道长度、取样体积、反应温度和酸度、试剂浓度等指标, 实现了每小时80个样本的在线分析。彭园珍等[24]以流动注射分析技术控制分析过程, 将硅钼蓝富集在固相萃取(solid-phase extraction, SPE)小柱上, 以少量NaOH溶液洗脱, 由可见分光光度计在线检测, 由此建立了流动注射-固相萃取-分光光度(flow injection-solid phase extraction-spectrophotometric, FI-SPE-Vis)测定水中痕量硅酸盐的新方法。GRUDPAN等[25]开发了流动注射分析停流技术, 有效避免了FIA要求反应速度需要比较快的局限性, 有效提高了检测方法的灵敏度。此后, 流动注射技术被大量应用于采矿业废水中偏硅酸(部分文献标注为可溶性二氧化硅)的测定[26-27]。SABARUDIN等[28]利用硅钼杂多酸根阴离子与罗丹明B在硝酸介质中形成一种离子缔合物, 结合流动注射技术以560 nm为激发波长, 580 nm为发射波长, 测量荧光强度的减弱, 建立了流动注射/荧光猝灭法测定超纯水中的硅含量的方法。由于流动注射法从系统设计上避免了硅钼黄比色液静置时间过长的问题, 相较于硅钼黄法, 其方法的稳定性更好。
ICP-OES/AES是一种可以对水溶液中元素精确定量的方法, 其检测偏硅酸的原理是将样品引入到高温的电感耦合等离子体中, 使样品中的硅原子被激发至高能态, 当硅原子回到基态时会发射出特征波长的光, 通过测量特征波长光的强度, 可以确定样品中硅元素的含量。
20世纪60年代, 美国FASSEL首次提出了ICP在原子光谱分析上的应用方法。此后, GREENFIELD等[29]和WENDT等[30]将ICP-OES技术应用于元素含量的检测中。栾燕等[31]在国内首次报道了采用ICP-AES测定矿泉水中偏硅酸含量的方法, 且其最低检出限可以达到0.005 μg/mL(以二氧化硅计), 以偏硅酸含量计算, 方法最低检出限可以低至0.065 mg/L, 结果显著优于硅钼黄分光光度法。此后, 姜莹等[32]也报道了采用ICP-OES测定饮用天然矿泉水中偏硅酸的方法, 在以251.6 nm作为特征吸收谱线的条件下, 检出限可以达到0.09 mg/L。赵雯玮等[33]验证了ICP-AES测定水中偏硅酸含量的能力, 其选用ICP-AES测定水中偏硅酸含量时选取288.158 nm为特征吸收谱线时, 响应值、精密度、线性均满足测定要求, 且测定结果与传统的硅钼黄法一致, 证明了ICP-AES具有省时、快速、高效、重现性好、准确度高等特点。张京等[34]对比了硅钼黄比色法和ICP-OES的检出限、精密度和准确度, 通过对实际地下水样品的加标回收实验来看, 两种方法精密度和准确度良好, 均满足地下水检测规范指标, 相比之下, ICP-OES在检出限、仪器精密度和准确度方面优于紫外分光光度法(ultraviolet spectrophotometry, UV)。谢永红[35]在前人的基础上探索了采用ICP-OES同时测定矿泉水界限指标中锌、锂、锶和偏硅酸的方法, 实现了对GB 8537—2018中4种界限指标的同时测定, 避免了按照GB 8538—2022中采用原子吸收光谱法、紫外可见分光光度法等多种仪器对每一种元素的单独测定, 大幅提高了饮用天然矿泉水界限指标的检测效率。
ICP-MS是20世纪80年代发展起来的新兴检测技术, 其通过将ICP离子源和质谱检测器结合, 完成样品中元素含量的分析。与ICP-OES/AES相比, ICP-MS的质谱检测器灵敏度更高, 检出限更低。其对于元素的检出限通常可达到ppt级甚至更低。
虽然ICP-MS拥有比ICP-OES/AES更高的灵敏度, 但因硅元素的质谱信号易受质量数相同的同位素阳离子干扰影响, 且排除同位素干扰的前处理操作较为复杂, 成本较高, 目前在偏硅酸检测中的应用仍然相对较少。HIOKI等[36]首次报道了采用ICP-MS测定海水中的可溶性硅, 通过采用离子排阻色谱对海水样品进行纯化后, 硅元素的检出限可低至0.0023 mg/L, 折合偏硅酸含量为0.0064 mg/L。该方法的6个样品的测试相对标准偏差为1.45%, 结果表现出极高的稳定性。NONOSE等[37]在前人的基础上增加了同位素稀释步骤, 其研究发现, 由于28Si+的质量与14N2+12C16O+的质量数相近, 而29Si+的质量与14N2H+12C16OH+的质量数相近, 检测硅元素的质谱信号易受这些阳离子的干扰, 采用同位素稀释技术, 通过加入已知含量的29Si+同位素示踪剂, 通过计算Si同位素比例变化计算Si元素含量, 可以有效避免其他质量数相近的阳离子对Si含量检测结果的影响。崔晓娇等[38]用ICP-MS实现了矿泉水界限指标中5种元素同时测定, 其使用二氧化硅作为硅元素的标准品, 通过测定28Si元素的含量来推算矿泉水中偏硅酸的浓度, 研究结果表明, 采用ICP-MS测定矿泉水中的偏硅酸, 回收率为89.2%~96.5%之间。与硅钼黄方法测定结果相比, 结果差异仅为2.97%, 证明了ICP-MS可以准确测定矿泉水中的偏硅酸含量, 再通过水中的硅元素的含量可以推算出水中溶解的偏硅酸含量。
离子色谱法检测偏硅酸主要是基于离子交换原理, 样品中的偏硅酸在碱性条件下呈盐态, 其中偏硅酸根阴离子在流动相的带动下与色谱柱中离子交换树脂发生交换作用, 通过树脂的亲和力差异做梯度洗脱, 实现偏硅酸根离子与其他离子的分离。最后通过电导检测器对流出的偏硅酸根离子进行检测。
刘肖等[39]采用阴离子色谱交换柱进行分离, 非抑制型电导离子色谱法检测, 直接进样测定矿泉水中硅酸盐(偏硅酸)含量, 方法检出限为0.2 mg/L, 加标回收率为92.5%~106.8%, 用该方法对市售11种饮用水中偏硅酸的含量进行检测, 结果均与商品化矿泉水包装标识值相符, 证明该方法可以准确有效检测偏硅酸含量。杨占强等[40]优化了非抑制型离子色谱法, 采用亲水性更强且柱容量较大的的 Dionex IonPacTM AS20色谱柱, 同时在流动相中增加60 mmol/L的甘露醇, 开发了测定矿泉水中偏硅酸和硼酸含量的方法, 优化条件后, 偏硅酸的方法检出限可低至0.078 mg/L, 回收率100.5%~102.7%, 方法成功测试了9种市售饮用矿泉水中的偏硅酸含量, 但作者也在研究中说明, 这种方法在超纯水等极低偏硅酸含量样品的检测中仍不适用。高翔等[41]采取非抑制型离子色谱法测定矿泉水中偏硅酸, 方法选用SH-Anion-3阴离子色谱柱搭配3.6 mmol/L Na2CO3淋洗, 对偏硅酸进行检测, 方法线性范围5~100 mg/L, 加标回收率99.57%~101.50%。
由于非抑制型电导检测法中偏硅酸的保留时间较短, 易受其他弱保留组分干扰, 当样品中偏硅酸含量较低时, 为了提高偏硅酸的检出效率, 控制背景离子对偏硅酸离子的噪音影响, 也有学者探索采用抑制性离子色谱, 通过在分析色谱柱后增加抑制器, 将高电导的流动相转变为低电导的物质, 提升样品中偏硅酸的相对电导值, 从而实现提高检测灵敏度的目的。李莎等[42]建立了一种抑制型离子色谱检测矿泉水中偏硅酸的方法, 方法检出限为0.15 mg/L, 相对标准偏差为0.554%~0.689%, 样品平均加标回收率为99.0%~102.2%, 方法在0.5~100 mg/L范围内具有良好的线性关系, 相关系数为0.99931。以上可以看出抑制型离子色谱法的检出限优于非抑制型, 当样品偏硅酸含量较低时, 建议优先采用抑制型离子色谱法进行测试。
除了上述方法外, 还有一些学者报道了通过液相色谱、排阻色谱等色谱方法对水中偏硅酸(可溶性硅)的检测方法。YOKOYAMA等[47]采用高效液相色谱柱同时测定水中硅酸盐与磷酸盐, 方法对偏硅酸的检出限低至0.007 mg/L(以二氧化硅计), 其原理是基于可溶性二氧化硅与钼酸铵在离子对液相色谱上反应生成黄色杂多钼酸盐, 采用紫外检测器在310 nm条件下测定。该方法虽然检出限较低, 但仪器和操作要求较高, 未见有同类研究和方法的推广应用报道。LI等[48]采用离子排阻色谱配备电导检测器, 开发了矿泉水、自来水、蒸馏水及海水中硅含量的测定方法, 水样经色谱柱分离后直接进入电导检测器进行含量检测, 方法的检出限为0.02 mmol/L, 折合偏硅酸1.56 mg/L。相较于液相色谱法, 其检出限偏高, 精确度也低于GB 8538—2022硅钼黄法的定量限1 mg/L和硅钼蓝法的定量限0.1 mg/L。
本文梳理了当前水中偏硅酸的主要检测方法, 包括分光光度法、流动注射分析法、电感耦合等离子体发射光谱法, 电感耦合等离子体质谱法、离子色谱法等, 并对各类方法的优缺点进行了深入分析。总体来看, 不同方法在灵敏度、稳定性、操作便捷性及适用场景上存在显著差异, 未来需结合技术革新与实际需求进一步优化检测体系。
作为国家标准方法, 分光光度法是应用最广泛的偏硅酸检测方法, 其中硅钼黄法具有操作简单、成本低的优势, 但其灵敏度较低(定量限1 mg/L), 且显色稳定性受时间、亚铁离子干扰等因素限制, 难以满足痕量检测需求。国家标准中的硅钼蓝法通过还原反应显著提升了灵敏度(定量限0.1 mg/L), 但其也存在步骤烦琐、显色波长选择争议等问题。流动注射分析法通过自动化进样与在线反应提升了检测效率与稳定性, 但其设备成本较高, 且方法开发需针对不同水质进行参数优化, 限制了其推广。ICP-MS具有高灵敏度(检出限低至0.0064 mg/L)及检测稳定性强的优势, 但仪器价格较昂贵, 且硅元素28Si+易受14N2+的质谱信号干扰。离子色谱法通过离子交换树脂的亲和力差异, 实现偏硅酸根离子与其他离子的分离, 方法报道的检出限为0.078~0.2 mg/kg, 与国家标准的硅钼蓝法的检出限相似, 但当样品中偏硅酸含量较低时, 矿泉水中的氯离子、亚硝酸根离子、氟离子等弱保留组分可能对影响测试的准确度。在众多方法中, ICP-OES凭借其高灵敏度、多元素联测、抗干扰性强及自动化程度高的特点, 成为偏硅酸检测的首选方法之一, 尤其适用于复杂基质样品和高通量检测需求。随着ICP-OES仪器的小型化[49]与成本降低, 其在环境监测、食品检测等领域的应用将进一步扩展。
值得注意的是, 现有方法多聚焦于总硅或偏硅酸盐的测定, 而天然矿泉水中偏硅酸的存在形态(如单体、寡聚体)及其生物有效性差异尚未被充分探讨[50]。未来需结合分子光谱或核磁共振技术, 深入解析偏硅酸的形态分布及其与健康效应的关联, 为水质评价提供更全面的科学依据。
  • 河北省方便食品技术创新中心绩效补助经费项目(22567697H)
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2025年第16卷第8期
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20250103005
  • 接收时间:2025-01-03
  • 首发时间:2025-07-19
  • 出版时间:2025-04-25
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  • 收稿日期:2025-01-03
基金
河北省方便食品技术创新中心绩效补助经费项目(22567697H)
作者信息
    今麦郎食品股份有限公司食品安全管理中心, 邢台 055350

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* 侯国友(1968—), 男, 硕士, 高级工程师, 主要研究方向为食品安全。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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