海鱼自然基质中汞和砷质量控制样品研制及在能力验证中应用

目的研制汞、砷质量控制样品,对承担国家食品安全风险监测工作的各级疾病预防控制机构实施能力验证计划。方法采用直接测汞(DMA)法和电感耦合等离子体质谱(ICP-MS)法分别测定广东省采集的16种海鱼肌肉中汞和砷含量,确定以深海网箱养殖的单条大型鞍带石斑鱼为原料,然后经选取肌肉、干燥、脱脂、粉碎等步骤制成鱼肉粉样品。采用单因子方差分析样品均匀性和t检验检查稳定性。结果所制备鱼肉粉样品的均匀性和稳定性均良好。采用该样品对193个实验室实施能力验证计划,检测总汞和总砷满意率分别为81.1%和80.2%,其中采用DMA测定总汞和ICP-MS测定总砷的满意率最高。结论该鱼肉粉样品可作为质量控制样品应用于实验室检测汞、砷能力验证。本研究可为海产食品基质标准物质的研制以及相关食品安全国家标准的修订提供科学参考。     

直接测汞仪测定食品中总汞

目的建立直接测汞仪测定食品中总汞的方法。方法采用直接测汞仪测定食品中的总汞,并对FAPAS 07322大豆粉样品采用直接测汞仪法、原子荧光光谱法、电感耦合等离子质谱法测定进行方法比对,结合FAPAS 07322能力验证报告对直接测汞仪法进行评价。结果直接测汞法在低浓度范围(0～20 ng)和高浓度范围(20～300ng)的相关系数均能达到0.999,方法检出限为0.07μg/kg,精密度小于8.0%,回收率范围为90.0%～103.5%。FAPAS 07322测定结果为323μg/kg, Z值为0.0,接近实验室比对中位值。结论直接测汞仪测定食品中的总汞,操作简便快捷,结果准确,适用于食品中总汞的分析。     

全自动测汞仪检测食品中总汞方法的建立与应用

本实验参照GB 5009.17-2014《食品中总汞及有机汞的测定》方法,确立了DMA-80全自动测汞仪测定汞含量的方法。实验测定了热解温度对实验方法的影响,采用土样标准物质测定标准曲线,确定线性方程,测定了本方法的检出限(需要的参数包括标准偏差SD和线性斜率B),并计算了此方法的精密度,还测定了样品(包括奶粉、牛奶)加标回收率。结果表明:本方法线性范围是0.28~10.12ng,绘制的标准曲线为y=17633x+2440.3,相关系数r~2=0.9967。检出限为0.015ng,加标回收率为108.77%~114.47%,相对标准偏差(RSD)处于0.4%~4.6%之间,在5.0%范围内。质控样品是由中国计量科学研究院生产的标准参考物质GBW 10018鸡肉,其测定值均在标准值范围内。     

测汞仪快速测定保健食品中的总汞含量

建立了一种固、液体食品中总汞含量快速检测方法。通过测汞仪内置的模块化干燥、热分解、催化还原、金汞齐化、冷原子吸收等组件对样品中汞进行一站式的检测,无需对样品进行传统的前处理,避免了样品中汞的污染与损失。该法根据汞浓度建立了高、低两条浓度范围(0~20 ng和20~800 ng)的标准曲线,具有检出范围宽(0~800 ng)、检出限低(LOD=0.06μg/kg)等特点。采用该法测定了固、液态等6种保健食品中总汞的含量,并与现行的食品中总汞的测定国家标准方法进行了比较,两种方法的检测结果无显著性差异,通过对标准物质的测定验证表明该法测定结果准确可靠。高、中、低三个浓度水平回收实验测得回收率为93.20~106.00%,回收结果令人满意。该方法可推荐作为食品、农产品等国家食品安全抽检工作的快速检测方法。     

直接进样测汞法测定不同粒径固体食品样品中总汞差异性分析

目的 比较直接进样测汞法对不同粒径的固体食品样品中总汞测定结果的差异性,考察其对固体样品粒径的要求。方法 取不同粒径的固体食品样品于镍舟上,直接进样测定,采用两种不同基质的有证标准物质进行质量控制,用统计学方法及相对均匀度因子（ HE）进行比较分析。结果 实验过程中两种不同基质的有证标准物质的测定值均在标准值范围内,表明测定的准确性。大米未过筛组均匀度较差,而食用菌A均匀度较好可全部通过40目筛,即粒径选择均在≤425 μm（或筛孔≥40目）时总汞含量的测定结果无显著性差异,且不同品牌测汞仪测定结果具有较好的一致性。结论 直接进样测汞法测定固体食品样品的方法简单可靠,但因对样品均匀性有较高的要求,需样品粒径≤425 μm（或筛孔≥40目）时才能保证测定结果的准确性。     

食品总汞测定中三种不同前处理方法的对比研究

本文使用《食品安全国家标准食品中总汞及有机汞的测定》（GB 5009.17—2021）第四法“冷原子光谱法”对胡萝卜、豆角、大米、芹菜等8种标准物质中的总汞进行测定。采用直接进样法、快速消解法与微波消解法3种不同方式对样品进行处理,使用DMA-80型测汞仪进行测定。结果表明,快速消解法测定结果最为准确,8种标准物质检测结果均在标示值范围内。     

牡丹花粉中4种重金属含量的测定与分析

目的 采用微波消解-原子吸收光谱法/原子荧光光谱法测定牡丹花粉中铅、镉、总汞、总砷含量,探明洛阳农博园地区牡丹花粉中4种重金属污染物状况。方法 选取6个主栽品种牡丹花粉样品,经微波消解后,采用原子吸收光谱法和原子荧光光谱法测定4种重金属污染物含量,并分析和评价测定结果。结果 铅、镉、总汞、总砷在一定浓度范围内线性关系良好,相关系数均大于0.998,方法检出限分别为 0.010、0.003、0.003、0.010 mg/kg,各元素的加标回收率在94.2%~109.4%之间。6个主栽品种牡丹花粉中均不同程度地检出了4种重金属污染物,方差分析结果显示,4种重金属元素含量的变异系数均大于10%,品种间差异均具有统计学意义。结论 本方法准确度高、精密度好。参考相关国家标准,6种牡丹花粉中重金属含量均符合要求,本研究为牡丹花粉资源的综合利用及牡丹花粉产品的开发提供数据支持。     

茶叶中总汞含量测定的样品前处理研究

目的研究优化茶叶中总汞含量测定时的样品前处理。方法参照GB 5009.17-2014《食品安全国家标准食品中总汞及有机汞的测定》前处理过程,采用正交试验对影响微波消解的温度、时间和功率因素进行研究,获得较优的样品前处理参数,以此对盲审样品进行验证。结果测定茶叶中总汞含量时,可采用样品与硝酸直接加热方式进行预处理,微波消解过程对总汞回收率影响的因子由大到小为温度、功率和时间;最佳微波消解参数为温度80℃、时间8 min和功率1200 W,微波消解后的样品不需挥酸操作可直接定容测定;在最优前处理工艺参数条件下,盲审样品测定结果与其公布值基本一致。结论此样品前处理方式基本满足茶叶中中总汞含量测定的需求。     

2012~2013年西藏地区食品中总汞含量 监测结果分析

目的调查西藏地区食品中总汞含量,提出消费警示,为市场监管提供依据。方法本文采用全自动测汞仪测定食品中总汞,样品无需做离线的湿化消解或复杂前处理,可全自动直接进样。共采集拉萨市、林芝地区、山南地区、日喀则地区、阿里地区市售9大类775份食品,进行总汞检测并分析结果。结果西藏地区食品中总汞污染状况较轻,超标率仅为2.06%,主要由汞污染事件引起,其余食品均符合国家标准,汞暴露健康风险低。结论西藏食品中总汞污染总体水平不高,符合国家标准限量要求,但需加强市售外地食品的监管。     

芹菜粉中总膳食纤维标准物质的研制

目的 使用芹菜粉研制天然食品中总膳食纤维标注物质。方法 经冷冻干燥、混匀、分装制备了芹菜粉中总膳食纤维标准物质。采F-检验评价标准物质的均匀性, 采用T检验(t-test)评价标准物质的长期和短期稳定性, 6家实验室统一采用酶重量对芹菜粉中总膳食纤维进行定值, 并对定值结果进行了不确定度评估。结果 芹菜粉标准物质均匀性、稳定性均符合标准物质定值技术要求。芹菜粉中总膳食纤维标准物质定值结果为 (29.9±2.3) g/100g, k=2。结论 该标准物质可用于天然食品中总膳食纤维的日常检测的质量控制。     

电感耦合等离子体质谱法测定大米中的铅、镉、汞残留量研究

目的建立大米中铅、镉、汞的测定方法.方法采用电感耦合等离子体质谱(ICP-MS).结果在0～20 ng/ml范围内铅的浓度与响应值呈良好的线性关系(r=0.9983,n=5);平均回收率为109.3%,RSD=5.6%,(n=6).在0～10ng/ml范围内镉的浓度与响应值呈良好的线性关系(r=0.999998,n=5);平均回收率为99.2%,RSD=6.5%,(n=6).在0～5 ng/ml范围内汞的浓度与响应值呈良好的线性关系(r=0.99998,n=6);平均回收率为91.2%,RSD=7.3%,(n=6).结论本法简便、灵敏、准确.     

Mercury in UK imported fish and shellfish and UK-farmed fish and their products

Total mercury concentrations were measured in fish and shellfish and their products imported into the UK and also in UK-produced farmed salmon and trout. Three hundred and thirty-six samples were collected using a two-stage sampling plan. The sample plan was weighted to reflect consumption, but with some bias towards fish that might accumulate higher levels of mercury, such as large predatory fish at the top of the food chain. The highest levels of total mercury were found in billfish (swordfish and marlin) and shark. Mercury concentrations in the five samples of fresh/frozen shark ranged from 1.006 to 2.200 mg kg -1 , all above the European Commission limit for the species, and concentrations in 20 samples of fresh/frozen billfish ranged from 0.153 to 2.706 mg kg -1 with 13 samples above the 1.0 mg kg -1 limit for the species. One sample of Antarctic ice fish was collected and had a mercury concentration of 0.664 mg kg -1 . The limit for this species was 0.5 mg kg -1 . One sample of fresh/frozen tuna out of the 20 collected had a mercury concentration above the limit of 1.0 mg kg -1 (1.5 mg kg -1 ), but all other fresh tuna samples were well within the regulatory limit (average 0.4 mg kg -1 ). Mercury concentrations in canned tuna were lower with concentrations on average half that measured in fresh/frozen tuna. Mercury concentrations in UK-farmed salmon and trout were relatively low. The maximum concentration found in 46 samples of fresh/frozen or smoked trout and salmon was 0.103 mg kg -1 .     

微波消解-氢化物发生双道原子荧光光谱法同时测定糖蜜中的砷和汞

建立了微波消解-氢化物发生双道原子荧光光谱法同时测定糖蜜样品中砷和汞的分析方法。实验探索了酸的种类比例、固液比、微波强度、消解时间等各种微波消解条件,并对工作条件进行了优化。仪表检出限为砷0.0704μg/L,汞0.0089μg/L;精密度为砷1.13%,汞0.49%;样品加标回收率为砷96.1%～107.6%,汞102.3%～105.1%。应用该方法对广西某制糖集团下属公司的糖蜜中砷和汞的含量进行了分析,结果令人满意。     

双色荧光定量检测大米中的汞

利用两条部分互补的富含胸腺嘧啶（T碱基）的单链核酸,结合氧化石墨烯及核酸染料SYBR GreenⅠ,采用同步荧光分析法,建立一种高灵敏度、高选择性的汞离子（Hg2＋）双色荧光定量检测方法。在优化条件下,Hg2＋浓度在5×10－10～500×10－10 mol/L之间时,SYBR GreenⅠ及Carboxy-X-rhodamine（ROX）总的荧光强度（ΔIT）与Hg2＋浓度（C）之间具有良好的线性关系,其拟合的回归方程为ΔIT = 2.121 3C＋10.536 0,方法检出限（3σ）为2×10－10 mol/L。该方法操作简单、检测速度快、选择性好、灵敏度高、重复性好、检出限低。将该方法应用于大米中汞的检测,获得了满意的结果。     

Mercury content of some wild edible mushrooms

 The mercury (Hg) content of 112 samples of common, wild edible mushrooms was analysed by atomic absorption spectrometry. The average Hg content of all the samples was 1.72 mg/kg dry mass (DM) but the Hg concentrations found in different taxonomic groups (genera and species varied) remarkably. Although different sampling locations obviously have an effect on the Hg concentration of sporocarps, we found evidence for a Hg-accumulating capacity of some taxonomic groups. In addition to Agaricus and Macrolepiota, where the phenomenon of mercury accumulation has already been described, our results indicate high Hg levels in samples of Lycoperdon perlatum (average 2.94 mg/kg DM) and in Lepista species (average 3.02 mg/kg DM). These data confirm the need for greater attention to be given to Hg levels in wild common mushrooms, especially to Hg-accumulating species. Received: 20 February 1997     

Mercury content of some wild edible mushrooms

 The mercury (Hg) content of 112 samples of common, wild edible mushrooms was analysed by atomic absorption spectrometry. The average Hg content of all the samples was 1.72 mg/kg dry mass (DM) but the Hg concentrations found in different taxonomic groups (genera and species varied) remarkably. Although different sampling locations obviously have an effect on the Hg concentration of sporocarps, we found evidence for a Hg-accumulating capacity of some taxonomic groups. In addition to Agaricus and Macrolepiota, where the phenomenon of mercury accumulation has already been described, our results indicate high Hg levels in samples of Lycoperdon perlatum (average 2.94 mg/kg DM) and in Lepista species (average 3.02 mg/kg DM). These data confirm the need for greater attention to be given to Hg levels in wild common mushrooms, especially to Hg-accumulating species. Received: 20 February 1997     

Mercury content and bio-concentration potential of Slippery Jack, Suillus luteus, mushroom

This study aimed to assess the total Hg intake due to the meals made of fruit bodies of wild-grown Slippery Jack (Suillus luteus) fungus, which is popular and numerous species in young the common pine tree (Pinus sylvestris) forests of the northern chemosphere with temporal climate. Total mercury content has been determined separately in 120 composite samples of 383 caps and stipes of Slippery Jack and in surface soil layer (0–10 cm; <2 mm fraction) underneath to fruit bodies. The material originated from eight spatially distant background (unpolluted) areas across of Poland and was collected in 2002–2007. Determination of mercury was by cold-vapour atomic absorption (CV-AAS) after direct sample matrix pyrolysis and further released mercury amalgamation and desorption from gold wool. Slippery Jack effectively accumulated Hg in fruit bodies. Depending on the area of mushrooms collection, the median values of Hg bio-concentration factor varied between 2.5 and 14 for caps and between 1.0 and 8.8 for stipes. For well-developed fruit bodies of Slippery Jack a majority of Hg occurs in caps, when compared to much smaller in size stipes. The means of Hg content varied between 0.095 ± 0.082 and 0.28 ± 0.07 μg/g in caps and between 0.045 ± 0.018 and 0.13 ± 0.03 μg/g dry weight in stipes. A meal consisting of 300 g caps (fresh weight) of Slippery Jack mushroom collected from unpolluted sites could constitute up to 14–40% of daily reference dose (RfD) value of mercury.     

Total Mercury, Inorganic Mercury and Methyl Mercury Determination in Red Wine

This study deals with the development of a method for total Hg, inorganic Hg and methylmercury (MeHg) determination in red wine by using flow injection-cold vapour generation–inductively coupled plasma mass spectrometry (FI-CVG-ICP-MS) and gas chromatography-ICP-MS (GC-ICP-MS). For Hg speciation analysis, a derivatization step was carried out using a 1% (m/v) sodium tetraphenylborate (NaBPh₄) solution, followed by extraction of Hg species and their quantification by GC-ICP-MS. The main parameters evaluated were the make-up gas flow rate, volume of the NaBPh₄ solution, time for derivatization reaction/analyte extraction and solvent used for Hg species extraction. Accuracy was evaluated by analyte recovery, whereas recoveries ranged from 99% to 104% for Hg(II) and MeHg. The limits of detection (LODs) for Hg(II) and MeHg were 0.77 and 0.80 μg L⁻¹, respectively. Wine from Argentina, Brazil, Chile and Uruguay were analysed. The wine samples were also acid digested for total Hg determination by FI-CVG-ICP-MS. The LOD of the method used for total Hg determination was 0.01 μg L⁻¹. The concentrations of Hg species in red wine measured by GC-ICP-MS were lower than the respective LODs. Only total Hg was detected in the analysed samples, where the highest concentration of Hg found was 0.55 ± 0.02 μg L⁻¹.     

LC-氢化物-ICP联用技术分析测定水产动物及其制品中汞的形态

本文将电感耦合等离子体发射光谱仪与高效液相色谱-氢化物发生相结合,建立一种简单、高效的分析方法用于检测水产动物及其制品中的甲基汞（MetHg）、乙基汞（EtHg）及无机汞（Hg2+）。采用微波酸提取对样品进行前处理,优化色谱条件,载液浓度等,进而验证方法的精密度、检出限、准确度、加标回收率。结果表明：当流动相中甲醇含量为5%,L-半胱氨酸浓度为0.10%时,分离效果、峰型和仪器响应值较好,基本消除汞的记忆效应。在7 min内实现了无机汞、甲基汞、乙基汞的分离。线性关系良好（r＞0.9990）,相对标准偏差（RSD%）＜10.00%,方法定量限分别为0.023、0.032和0.038 mg/kg。以鱼类、贝类、甲壳类三种基质样品进行加标回收实验,回收率在82.50%~98.40%之间,采用两种水产动物标准物质BCR463和TORT-3验证了方法的准确性好。本方法前处理简单、分离效果、精密度好、准确度高,适用于水产动物及其制品中汞形态的分析测定,为汞的形态分析研究提供了一种新的方法依据。     

Mercury in Common Chanterelles mushrooms: Cantharellus spp. update

This paper reports the results of the determination of Hg contents of Common Chanterelles (Cantharellus cibarius) Fr. and surface soil layer (0–10 cm) underneath the fruiting bodies collected from 14 spatially distant areas across Poland between 1998 and 2008. Cantharellus mushrooms are important wild foods that are popular in Europe. The Hg contents of soils and Common Chanterelles showed different distributions, depending on the area studied. The range of Hg contents of the mushroom fruiting bodies was 18–66 ng/g dry weight with the highest mean contents of 46 ± 15 ng/g (range 23–66 ng/g) and 46 ± 13 ng/g (34–61 ng/g) observed for pristine areas of Podlasie land at the Bia?owie?a Forest and Wielkopolska land near the Pora?yn sites, respectively, and low concentration of 27 ± 8 ng/g (range 21–56 ng/g) observed for the Kujawy land at the Tuszynki site. The mean Hg levels in soil varied from 8 ± 6 ng/g (4–21 ng/g) for Kujawy land at the Tuszynki site to 200 ± 29 ng/g (145–240 ng/g) for Ma?opolska land at the high Tatra Mountains area of Zakopane. The mean soil Hg at the Zakopane site is approximately 25 times the concentration of Kujawy land, Tuszynki. Mercury bioaccumulations were in general low with the mean bioconcentration factor (BCF) ranging from 0.20 ± 0.05 to 3.8 ± 1.7 (overall range of 0.1–5.9). The Hg in soils and fruiting bodies of the present study are within acceptable ranges. The consumption of 300 g of popular Common Chanterelles from any of the investigated regions in Poland would not result in exposure to Hg that is in excess of the maximum weekly dose recommended by the WHO. The estimated dietary exposures to Hg for consumers of this mushroom were calculated and are shown to be below the guidelines for safe exposures. Also reviewed are published data on Hg and MeHg in C. cibarius and 11 other species of the Cantharellus genus collected worldwide.