液相色谱-氢化物发生-原子荧光光谱法测定干制食用菌中5种砷形态

目的 建立液相色谱-紫外消解-氢化物发生-原子荧光光谱法(liquid chromatography-ultraviolet digestion-hydride generation-atomic fluorescence spectrometry,LC-UV-HG-AFS)测定干制食用菌中砷甜菜碱(AsB)、砷酸根[As(Ⅴ)]、亚砷酸根[As(III)]、一甲基砷(MMA)和二甲基砷(DMA)的分析方法。方法 样品用水于60 ℃水浴超声提取1.5 h,离心10 min取上清液,经0.45 ?m滤膜过滤。采用Hamilton PRP-X100阴离子交换柱(250 mm×4.1 mm,10 μm),以8 mmol/L磷酸氢二铵(pH=8.5)为流动相进行分离,用LC-UV-HG-AFS法测定5种砷形态。结果 AsB、MMA、DMA和As(III)在2.5～200.0 μg/L范围内线性关系良好,As(Ⅴ)在5.0～200.0 μg/L范围内线性关系良好,5种砷形态标准曲线相关系数均大于0.999;5种砷形态加标回收率为85.0 %～107.0%,相对标准偏差均小于5.0%;AsB、MMA、DMA、As(III)和As(Ⅴ)的检出限分别为0.02、0.02、0.01、0.02和0.03 mg/kg,定量限分别为0.04、0.04、0.03、0.06和0.08 mg/kg。结论 对干制食用菌分析表明,食用菌中无机砷含量较低,砷含量高的食用菌主要以AsB为主。所建方法简便、准确、快速,适用于干制食用菌中AsB、MMA、DMA、As(III)和As(Ⅴ)的检测。     

高效液相色谱-电感耦合等离子体质谱法测定蚝油类调味品中5种砷形态

目的 采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP/MS)联用技术对蚝油类调味品中砷甜菜碱(AsB)、亚砷酸根[As(Ⅲ)]、二甲基砷(DMA)、一甲基砷(MMA)和砷酸根[As(Ⅴ)]5种砷形态进行分析方法研究.方法 蚝油类样品采用1％硝酸90℃热浸提3 h,提取液以8 000 r/min离心10 min...     

南极磷虾油脱砷效果

以南极磷虾粗油为原料,研究其脱砷方式、脱砷工艺参数及残存砷的存在形式。结果表明,最佳活性沸石类型为钠型沸石,脱砷工艺参数为料液质量比(油与沸石) 1∶0.3、脱砷时间4 h、脱砷温度50℃。该条件处理后的南极磷虾油透明度较高,色泽较浅,品质较好;经ICP-MS检测,脱砷后的南极磷虾油中共检出6种砷化合物,其中砷甜菜碱(AsB)的含量最高,有机砷含量占总砷含量的95.69%,南极磷虾油的食用安全性高。     

食品中砷的形态分析研究进展

砷是一种公认的有毒有害物质,现在相关研究中常涉及的砷形态包括亚砷酸盐(arsenite,AsⅢ)、砷酸盐(arsenate,AsⅤ)、一甲基砷酸(monomethyl arsenic acid,MMAⅤ)、二甲基砷酸(dimethyl arsinic acid,DMAⅤ)、砷甜菜碱(arsenobetaine,AsB)以及砷胆碱(arsenocholine,AsC)。砷的形态与其生物可给性、毒性密切相关,烹调过程能够影响食品中砷的形态,进而可能影响到砷对人体健康的风险性。因此,建立食品中砷形态分析的检测方法具有十分重要的意义。本文对砷的形态分析的检测方法及研究现状进行了综述,重点介绍了溶剂提取及微波、超声辅助提取等前处理方法以及砷的形态分析方法在食品中的应用,同时对砷的形态在烹调过程中的变化进行了阐述,并对未来发展方向进行了展望。     

高效液相色谱-电感耦合等离子体质谱法测定保健食品类袋泡茶中5种砷形态

目的采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP/MS)联用技术建立保健食品类袋泡茶浸泡液中亚砷酸根[As(Ⅲ)]、砷酸根[As(Ⅴ)]、一甲基砷酸(MMA)、二甲基砷酸(DMA)和砷甜菜碱(AsB)5种砷形态的分析方法。方法样品经热浸提后,采用Dionex IonPac AS19(4 mm×250 mm,10μm)阴离子交换柱,30 mmol/L碳酸铵(pH=9.5)为流动相等度洗脱,10 min内进行5种砷形态的分析测定。结果 5种砷形态的浓度在0.2～300μg/L范围内线性良好,相关系数(r)均0.999,检出限为0.04～0.08μg/L,采用精密度考察方法重复性,相对标准偏差(RSD)均5%,加标回收率在80.3%～121.1%之间。结论本方法适用于保健食品类袋泡茶浸泡液中砷形态的测定,试验表明保健食品类袋泡茶中砷形态主要以As(Ⅲ)和As(Ⅴ)为主,应关注其无机砷的风险性。     

大米中的砷形态对小鼠各组织中砷代谢分布及其病理特征的影响

旨在探讨经口暴露的大米砷形态引起的砷毒性以及其生物转化。实验以四个砷含量剂量组(C、S:0.91 mg/kg、M:9.1 mg/kg和H:30 mg/kg)喂养模拟大米砷形态饲料30 d,通过ICP-MS和HPLC-ICP-MS测定小鼠肠、血、肝脏和肾脏中的砷含量及砷形态(iAsⅢ、iAsⅤ、MMA、DMA和AsB)分布;H&E染色后光学显微镜下观察小鼠肠组织、肝脏和肾脏的组织学变化。结果显示,在C、S、M和H中,血的总砷浓度分别为5.33、8.24、55.75和196.49μg/kg;肝的总砷浓度分别为14.34、32.70、237.10和708.74μg/kg;肠中五种砷形态浓度之和分别为27.97、163.12、892.78、3085.325μg/kg;肾中五种砷形态浓度之和分别10.38、25.79、245.85、1656.14μg/kg。肠中主要的砷形态为iAsⅢ和DMA,血液中有机砷与无机砷的比值随暴露剂量升高而增加,肝脏和肾脏中主要的砷形态为DMA。与对照组比较,各实验组小鼠肠组织、肝脏和肾脏出现的病理损伤程度随砷暴露剂量的增加而深化,在H组中最明显。本研究表明,短期的大米砷暴露对机体代谢组织无明显损伤,且砷在组织中的累积较少;而高剂量的大米砷暴露将对机体病理结构造成严重损伤;提示长期低剂量的大米砷暴露也可能对机体产生损害。     

深圳市盐田区海产品总砷及砷形态调查研究及风险评价

采用电感耦合等离子体质谱法(ICP/MS)检测海产品的总砷含量,液相色谱-电感耦合等离子体质谱联用(HPLC-ICP-MS)检测海产品5种砷形态含量。在被检测的180份海产品中,168份海产品的总砷含量高于0.5mg/kg,所占比例为93.3%,均值为9.43mg/kg。该168份海产品的砷形态(As B、AsⅢ、AsⅤ、MMA、DMA)检测结果为无机砷(AsⅢ与AsⅤ)含量均低于定量限0.06mg/kg;检出含量高于0.5mg/kg的砷甜菜碱(As B)124份(73.8%),均值为7.05mg/kg;二甲基砷(DMA)49份(29.2%),均值为0.25mg/kg;一甲基砷(MMA)未检出。结果显示,无毒的As B含量明显高于低毒的DMA(P0.05),含量高于0.5mg/kg的As B检出比例也明显高于DMA(P0.05),表明本地区海产品安全风险较低,食用安全性有保障。     

烟草及其制品中砷的形态分析

为了测定烟草中砷(As)的形态,采用超声溶剂萃取、高效液相色谱(HPLC)与电感耦合等离子体质谱(ICP-MS)联用技术建立了亚砷酸[As(III)]、砷酸[As(V)]、二甲基胂酸(DMA)、甲基胂酸(MMA)、砷甜菜碱(AsB)和砷胆碱(AsC)6种形态As的分离分析方法。结果表明:采用Hamilton PRPX-100(250 mm×4.1 mm,10μm)阴离子交换柱、15 mmol/L(NH4)2HPO4(pH6.0)等度洗脱,6种不同形态As在15 min内实现了基线分离,线性范围不小于两个数量级,检出限0.44~0.98μg/L,加标回收率85.19%~87.31%,相对标准偏差(RSDs,n=5)2.45%~3.56%。烟草中As含量较低,且部分以低毒的DMA、MMA形态存在;超声溶剂提取能同时提取烟草中的有机As和无机As,较客观地反映样品中As的形态分布。该方法准确、可靠,适合于评价烟草中As的形态,可为烟草的安全性评价提供参考。     

微波辅助提取—高效液相—电感耦合等离子体质谱法测定生米与熟米中各形态砷的含量

建立微波辅助提取—高效液相—电感耦合等离子体质谱(MAE—HPLC—ICP—MS)测定大米中各种形态砷含量的方法。通过对微波温度、时间、功率进行条件优化,在80℃、600 W、20min的微波条件下可得到最佳提取效果。As(Ⅲ)、DMA、MMA、As(Ⅴ)4种砷形态的标准曲线线性良好,样品加标回收率在86.15%~109.80%。所建方法与GB/T 5009.11—2014比较发现:两种方法测得的As(Ⅲ)、DMA、As(Ⅴ)含量无显著差异,而所建方法测得的MMA含量则高于GB/T 5009.11—2014的。根据所建方法分别测定生米和熟米中各种形态砷的含量,发现大米经过蒸煮后As(Ⅲ)和DMA比重下降,而MMA和As(Ⅴ)比重上升,总砷浓度下降了8.77%。     

毛细管电泳-电感耦合等离子体质谱(CE-ICP-MS)联用测定干海产品中的六种砷形态化合物

采用电感耦合等离子体质谱(ICP-MS)测定了鱿鱼、银鱼、沙丁鱼、虾、牡蛎、蛤蜊、紫菜、羊栖菜、海带、浒苔10种干海产品中的砷总量,建立了毛细管电泳(CE)与ICP-MS联用测定亚砷酸盐As(III)、砷酸盐As(V)、甲基砷酸(MMA)、二甲基砷酸(DMA)、砷甜菜碱(AsB)和砷胆碱(AsC)六种砷形态化合物的分析方法。结果发现除了浒苔其余干海产品中砷总量均超出了无机砷允许限值(GB 2762-2005),形态分析结果表明干海产品中主要是有机砷,萃取液中无机砷含量仅占砷总量的0~15.2%。该方法简单方便、快速,样品消耗量少,而且具有较好的准确性,适用于其他生物样品中砷形态化合物的分析。     

液相色谱-电感耦合等离子体-质谱法分析海藻碘浓缩液中砷形态

目的 建立液相色谱-电感耦合等离子体质谱法(liquid chromatography-inductively coupled plasma mass spectrometry, LC-ICP-MS)测定海藻碘浓缩液中6种不同形态砷化合物的分析方法。方法 单因素实验确定对不同形态砷化合物LC-ICP-MS的分离条件, 包括流动相浓度、pH及洗脱方式。以总砷提取效率的高低评价三种不同的提取砷化合物的方法, 确定最佳方法。结果 以稀硝酸浸提的前处理方法的提取效果最佳, 提取效率为84.28%~92.99%;以25 mmol/L pH8.0磷酸二氢铵溶液和水作为流动相, 采用梯度洗脱的方式, 可以将6种砷形态完全分离,结果显示6种海藻碘样品中砷甜菜碱AsB含量较多, 而亚砷酸盐As(III)、砷酸盐As(V)和二甲基砷酸DMA含量较少, 未检测出砷胆碱AsC和一甲基砷酸MMA, 样品有毒砷含量占浓缩液总砷含量的2.01%~3.69%, 本方法加标回收率在80.4%~101.5%之间。结论 海藻碘浓缩液中砷形态的主要存在形式为AsB,本方法准确、简单,适合海藻碘浓缩液中砷形态分析。     

Determination of 6 arsenic species present in seaweed by solvent extraction,clean-up,and LC-ICP/MS

The analytical method was developed for the speciation of 6 arsenic species [As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), and arsenocholine (AsC)] in sea mustard (Undaria pinnatifida), dashima (Laminaria japonica), and laver (Porphyra tenera) of seaweed. After extraction under sonication with a solution of 50%(v/v) methanol in 1% HNO₃ and subsequent clean-up with anion-exchange cartridge, arsenic species were quantified by liquid chromatography with inductively coupled plasma-mass spectrometry. The ion-exchange cartridge is effective to remove a lot of interference. The gradient elution method was used for high resolution of arsenic species and the optimum pH of mobile phase is 6.0 and 6.2. Limit of detection and quantification were set at 0.06–0.12 and 0.20–0.40 ng/mL, respectively. Overall recoveries of arsenic species from fortified samples in seaweed were 81.1–118.8%, except for AsB and AsC in dashima and laver. This proposed method could be useful for quantification and speciation of arsenic species in seaweed as well as other foodstuffs.     

Arsenic speciation in plankton organisms from contaminated lakes: transformations at the base of the freshwater food chain

The two complementary techniques high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and X-ray absorption near edge structure (XANES) analysis were used to assess arsenic speciation in freshwater phytoplankton and zooplankton collected from arsenic-contaminated lakes in Yellowknife (Northwest Territories, Canada). Arsenic concentrations in lake water ranged from 7 μg L(-1) in a noncontaminated lake to 250 μg L(-1) in mine-contaminated lakes, which resulted in arsenic concentrations ranging from 7 to 340 mg kg(-1) d.w. in zooplankton organisms (Cyclops sp.) and from 154 to 894 mg kg(-1) d.w. in phytoplankton. The main arsenic compounds identified by HPLC-ICP-MS in all plankton were inorganic arsenic (from 38% to 98% of total arsenic). No other arsenic compounds were found in phytoplankton, but zooplankton organisms showed the presence of organoarsenic compounds, the most common being the sulfate arsenosugar, up to 47% of total arsenic, with traces of phosphate sugar, glycerol sugar, methylarsonate (MMA), and dimethylarsinate (DMA). In the uncontaminated Grace Lake, zooplankton also contained arsenobetaine (AB). XANES characterization of arsenic in the whole plankton samples showed As(V)-O as the only arsenic compound in phytoplankton, and As(III)-S and As(V)-O compounds as the two major inorganic arsenic species in zooplankton. The proportion of organoarsenicals and inorganic arsenic in zooplankton depends upon the arsenic concentration in lakes and shows the impact of arsenic contamination: zooplankton from uncontaminated lake has higher proportions of organoarsenic compounds and contains arsenobetaine, while zooplankton from contaminated area contains mostly inorganic arsenic.     

Sequential extraction combined with HPLC–ICP-MS for As speciation in dry seafood products

A sequential extraction procedure followed by HPLC–ICP-MS analysis was developed for the speciation and quantization of arsenic species in dry seafood products (DSPs). The extraction process involved three major steps, which produced respectively three As fractions: non-polar (As_nonpolar), polar (As_polar) and inorganic arsenic species (As_inorganic). The extraction efficiency (EE%) is in the range of 87–115%. As_nonpolar is 0.6–10.2% of total arsenic in DSPs, which is served as the index of level of arsenolipid. For As_polar and As_inorganic, a hyphenated HPLC–ICP-MS technique was established for the separation and quantification of six arsenic species including arsenobetaine (AsB), arsenocholine (AsC), arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). The results indicate that AsB and AsV are the two dominate species in DSPs, while all other species are present in relatively low concentrations. The recovery efficiency of 77–02.8% could be obtained with spike recovery test in this two-steps extraction.     

超声辅助提取-高相液相色谱-电感耦合等离子体质谱法测定香菇中6种形态砷化合物

建立一种同时测定香菇中6 种形态砷化合物（亚砷酸根、砷酸根、一甲基砷酸、二甲基砷酸、砷甜菜碱、砷胆碱）的超声辅助提取-高效液相色谱-电感耦合等离子体质谱（high performance liquid chromatography-inductivelycoupled plasma mass spectrometry,HPLC-ICP-MS）分析方法。选取0.3 mol/L乙酸溶液作为提取剂,超声辅助提取香菇样品中的砷化合物,选用Hamilton PRP X-100阴离子交换柱,25 mmol/L磷酸二氢铵和水作为流动相进行梯度洗脱,经HPLC-ICP-MS进行分离和定量分析。结果表明,在优化实验条件下,6 种形态砷化合物在0～50 μg/L范围内线性良好,相关系数R2均在0.998 0以上,检出限为0.31～0.59 μg/L,相对标准偏差为1.6%～3.7%,加标回收率在94.30%～102.75%之间。4 种处理方式后的香菇样品的测定结果显示,无机砷是主要的砷化合物,占总砷含量的48.68%～64.25%。方法灵敏度高,前处理简单高效,可以有效地分析香菇样品中不同形态的砷化合物。     

Quantification of four arsenic species in fruit juices by ion-chromatography-inductively coupled plasma-mass spectrometry

A method using ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) for the quantification of arsenic species in fruit juices has been developed and validated. The method is capable of quantifying four anionic arsenic species - arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) - in the presence of unretained species such as arsenobetaine (AsB). Method validation was based on repeatability, analysis of reference materials, recovery of fortified samples, and determination of detection and quantification limits. The method was tested for use with apple, pear, cranberry, grape (red, white and purple) juices, as well as several juice blends. Limits of detection were 0.35, 0.41, 0.45 and 0.70?μg?kg(-1) for As(III), DMA, MMA and As(V), respectively. Chromatographic recovery was good for most samples (90-107% compared to total arsenic), though recovery for some grape juice samples was lower (67-78%).     

Quantification of four arsenic species in fruit juices by ion-chromatography–inductively coupled plasma–mass spectrometry

A method using ion chromatography–inductively coupled plasma–mass spectrometry (IC–ICP–MS) for the quantification of arsenic species in fruit juices has been developed and validated. The method is capable of quantifying four anionic arsenic species – arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) – in the presence of unretained species such as arsenobetaine (AsB). Method validation was based on repeatability, analysis of reference materials, recovery of fortified samples, and determination of detection and quantification limits. The method was tested for use with apple, pear, cranberry, grape (red, white and purple) juices, as well as several juice blends. Limits of detection were 0.35, 0.41, 0.45 and 0.70?µg?kg^?1 for As(III), DMA, MMA and As(V), respectively. Chromatographic recovery was good for most samples (90–107% compared to total arsenic), though recovery for some grape juice samples was lower (67–78%).     

海产品中的砷及其代谢机制的研究进展

海产品中的砷通过食物链富集的方式进入人体。海产品中检测出的砷形态有三价的亚砷酸盐(As(III))、五价的砷酸盐(As(V))、砷胆碱(As C)、砷甜菜碱(As B)、砷糖、砷脂等。各种形态的砷通过不同代谢途径产生不同的代谢产物,从而表现出不同的毒性。砷的形态主要是通过高效液相色谱与电感耦合等离子体质谱仪的联用(HPLC-ICP-MS)来测定的。有机砷中砷胆碱(As C)的代谢产物为砷甜菜碱(As B)和砷脂;砷甜菜碱(As B)经尿液直接排出;不同的砷脂代谢产物不一样;砷糖的代谢产物至少12种,最主要的是五价的二甲基砷酸盐(DMA(V))。无机砷(包括砷酸盐和亚砷酸盐)最后代谢产物为五价的二甲基砷酸盐(DMA(V))和三价的二甲基亚砷酸盐(DMA(III))。海产品经过不同烹调处理后,其总砷浓度或多或少都有增加,砷形态也有变化,部分加工会导致毒性增加。对于消费者来说,注意饮食习惯包括海产品摄入量,摄入间隔,日常营养元素摄入与烹调方式的选择等是预防过量摄入有毒砷形态的有效手段。     

高效液相色谱-氢化物发生原子荧光联用法检测 不同基质食品中的砷含量及其形态

目的建立高效液相色谱-氢化物发生原子荧光联用法检测大虾、金枪鱼、虾油、大米和菠菜等不同基质食品中的砷含量及其化学形态。方法将大虾、金枪鱼、虾油、大米和菠菜样品采用HNO_3(0.15 mol/L)浸提,高效液相色谱-氢化物发生原子荧光联用法进行砷形态的研究,并用湿法消解-原子荧光光谱法进行总砷含量的测定。结果所测大虾、金枪鱼、虾油、大米、菠菜样品总砷含量为0.23~4.68 mg/kg,有机砷含量为0~3.9 mg/kg。海产品中主要砷形态为2种砷化物:二甲基砷(DMA)和砷甜菜碱(AsB);大米及菠菜样品中主要的砷形态为:三价砷As(Ⅲ)、二甲基砷(DMA)和五价砷As(Ⅴ)。结论该方法操作简单,灵敏度高,重现性好,适用于食品中砷形态含量的定量检测。