HPLC-ICP-MS测定泽泻、金银花、鸡血藤中可溶性价态砷及残留限度

目的 建立高效液相色谱-电感耦合等离子质谱(HPLC-ICP-MS)测定方法,分析金银花、泽泻、鸡血藤中4种不同价态砷,评估泽泻、金银花、鸡血藤中4种价态砷的残留情况,为制定相关残留限度提供依据。方法 采用0.05 mol·L^-1 EDTA溶液超声提取样品中可溶性砷,采用HPLC-ICP-MS分析样品中可溶性砷的形态。结果 As(Ⅲ)、DMA、MMA、As(Ⅴ)在5~200 μg·L^-1内线性良好,平均回收率(n=9)为105.1％~108.4％,方法检测限为0.01 mg·kg^-1。泽泻检出少量As(Ⅲ)、As(Ⅴ),金银花检出少量As(Ⅲ)、DMA、As(Ⅴ),鸡血藤则均未检出As(Ⅲ)、DMA、MMA、As(Ⅴ)。结论 该方法操作简便、结果准确、重复性好,能满足4种不同价态砷的残留限度分析。     

Arsenic speciation analysis of urine samples from individuals living in an arsenic-contaminated area in Bangladesh

Objectives

Chronic inorganic arsenic (iAs) exposure currently affects tens of millions of people worldwide. To accurately determine the proportion of urinary arsenic metabolites in residents continuously exposed to iAs, we performed arsenic speciation analysis of the urine of these individuals and determined whether a correlation exists between the concentration of iAs in drinking water and the urinary arsenic species content.

Methods

The subjects were 165 married couples who had lived in the Pabna District in Bangladesh for more than 5 years. Arsenic species were measured using high-performance liquid chromatography and inductively coupled plasma mass spectrometry.

Results

The median iAs concentration in drinking water was 55 μgAs/L (range <0.5–332 μgAs/L). Speciation analysis revealed the presence of arsenite, arsenate, monomethylarsonic acid (MMA), and dimethylarsinic acid in urine samples with medians (range) of 16.8 (7.7–32.3), 1.8 (<0.5–3.3), 13.7 (5.6–25.0), and 88.6 μgAs/L (47.9–153.4 μgAs/L), respectively. No arsenobetaine or arsenocholine was detected. The concentrations of the 4 urinary arsenic species were significantly and linearly related to each other. The urinary concentrations of total arsenic and each species were significantly correlated with the iAs concentration of drinking water.

Conclusions

All urinary arsenic species are well correlated with each other and with iAs in drinking water. The most significant linear relationship existed between the iAs concentration in drinking water and urinary iAs + MMA concentration. From these results, combined with the effects of seafood ingestion, the best biomarker of iAs exposure is urinary iAs + MMA concentration.     

高效液相色谱-电感耦合等离子体质谱法测定食品中6种常见的砷形态

目的 建立食品中6种常见砷形态的高效液相色谱-电感耦合等离子体质谱（HPLC - ICP - MS）测定方法。方法 样品采用50%甲醇水溶液和10%甲醇依次提取, Hamilton X - 100色谱柱分离, 乙酸钠（NaAc） -硝酸钾（KNO3） -磷酸二氢钠（NaH2PO4） - 乙二胺四乙酸二钠（EDTA·2Na）与纯水流动相体系梯度洗脱,电感耦合等离子体质谱法（ICP - MS）检测。结果 6种砷形态12 min内完全分离。方法相关系数大于0.999,方法检出限为0.005 ～ 0.010 mg/kg,提取效率为94.80%～110.00%,回收率为84.70%～114.00%,精密度为0.88%～4.59%。结论 本法简便、快捷、精密和准确,可用于食品中6种砷形态的测定。     

苯胂酸类药物检测技术研究进展

苯胂酸类药物作为一种重要的有机砷制剂,由于能够刺激动物生长、改善禽肉质、增加饲料利用率等功效而被作为畜禽饲料添加剂使用。本文主要综述了有关这类药物的检测技术,重点介绍了目前使用较广泛的检测技术的特点及其存在的主要问题,并提出了今后苯胂酸类药物检测技术的发展方向。     

仁青芒觉中可溶性砷形态的HPLC-ICP-MS研究

目的:采用HPLC-ICP-MS对藏药仁青芒觉中可溶性砷的形态进行研究。方法:采用Agilent G3154A阴离子交换柱,以0.2 mmol.L-1 EDTA和2 mmol.L-1磷酸二氢钠的溶液(pH 6.0)为流动相,流速1.0 mL.min-1,测定了仁青芒觉中砷的形态。前处理选择微波萃取,比较了1%盐酸、1%硝酸、2%醋酸、50%甲醇不同萃取剂的提取效率。结果:仁青芒觉在不同提取液中砷的形态主要以As(Ⅲ)和As(V)的形式存在,且1%盐酸、1%硝酸的提取效率较高。As(Ⅲ)和As(V)检出限(S/N=3)分别为0.39 ng.g-1和0.72 ng.g-1,样品加标平均萃取回收率(n=3)分别为95.6%和85.3%,精密度试验的RSD(n=8)分别为2.0%和3.2%。结论:藏药仁青芒觉中可溶性砷形态的研究,为藏药中砷的毒理学研究提供了依据。     

Essential and non-essential elements in Brazilian infant food and other rice-based products frequently consumed by children and celiac population

Rice and its derivatives are important source of essential and non-essential elements. Essential elements as cobalt (Co) and selenium (Se) are vital for human homeostasis. However, non-essential elements such as arsenic (As), cadmium (Cd) and lead (Pb) may be present in rice-based food and consequently, people can be exposed—especially children and the celiac population. This study aimed to determine essentials and non-essentials elements in rice-based products and baby food and also to evaluate nutritional risk by estimating the daily intake of non-essential elements. Regarding essential elements, Co and Se presented the highest concentrations in rice flour (56 μg kg⁻¹) and porridge (254 μg kg⁻¹), respectively. For non-essential elements, the highest concentrations of As, Cd and Pb were 104 μg kg⁻¹ (porridge), 16 μg kg⁻¹ (flour), and 188 μg kg⁻¹ (bread), respectively. Total As concentration in Brazilian rice-based baby food was <29 μg kg⁻¹. However, As-speciation revealed inorganic-As (i-As) as the main specie. The highest estimated daily intake of Cd, Pb and i-As were 1.37 (rice-based baby food); 10.39 (pasta); and 3.34 (pasta) μg d⁻¹, respectively. Therefore, continuous food monitoring for nutritional and toxicological purpose is necessary, especially concerning these particular populations and discussions for maximum levels of non-essential elements.     

Occurrence,speciation analysis and health risk assessment of arsenic in Chinese mitten crabs (Eriocheir sinensis) collected from China

Arsenic (As) is a major hazardous element in natural environments, and arsenic pollution is becoming an issue of concern worldwide. The more toxic inorganic arsenic, such as trivalent arsenite As(Ⅲ) and pentavalent arsenate As(Ⅴ), which normally can transform to organic arsenic compounds, such as arsenobetaine (AsB), arsenocholine (AsC), monomethyl arsenic acid (MMA), dimethyl arsenic acid (DMA), trimethyl arsenic acid (TMA), arsenosugars and arsenolipids. In this study, a total of 2130 individuals of Chinese mitten crabs were collected from seven locations and mixed to 71 samples. Total arsenic and six major species (AsC, AsB, DMA, MMA, As (Ⅲ), and As (Ⅴ)) were determined by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), respectively. The target hazard quotient (THQ) was utilized to evaluate the human health risk. The total arsenic concentration and totals for the six arsenic forms are 0.25–1.66 mg/kg and 0.05–1.19 mg/kg wet mass, respectively. Except for HH and LH, the six arsenic species concentrations accounted for more than 50.0 % of the total arsenic. The less toxic AsB is the most predominant in crabs, comprising 50.0 %–90.0 % of the sum of six types of arsenic. The more toxic inorganic arsenic only range from 0.01 to 0.21 mg/kg wet mass, much less than the limit content of 0.50 mg/kg inorganic As in crustacea. The THQ values of inorganic arsenic through the consumption of Chinese mitten crabs are estimated, and the values are all less than 1, indicating that intaking Chinese mitten crabs collected from China will not cause an appreciable hazard risk to human health.     

Understanding arsenic metabolism through a comparative study of arsenic levels in the urine, hair and fingernails of healthy volunteers from three unexposed ethnic groups in the United Kingdom

Very little is known about arsenic (As) metabolism in healthy populations that are not exposed to high concentrations of As in their food or water. Here we present a study with healthy volunteers from three different ethnic groups, residing in Leicester, UK, which reveals statistically significant differences in the levels of total As in urine and fingernail samples. Urine (n = 63), hair (n = 36) and fingernail (n = 36) samples from Asians, Somali Black-Africans and Whites were analysed using inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectroscopy (GF-AAS). The results clearly show that the total concentrations of As in urine and fingernail samples of a Somali Black-African population (urine 7.2 microg/g creatinine; fingernails 723.1 microg/kg) are significantly (P < 0.05) different from the Asian (urine 24.5 microg/g creatinine; fingernails 153.9 microg/kg) and White groups (urine 20.9 microg/g creatinine; fingernails 177.0 microg/kg). The chemical speciation of As in the urine of the three groups was also measured using high performance liquid chromatography coupled to ICP-MS. This showed that the proportion of the total urinary As present as dimethylarsenate (DMA) was higher for the Somali Black-African group (50%) compared to the Asians (16%) and Whites (22%). However, there was no significant difference (P > 0.05) in the level of As in the hair samples from these three groups; Somali Black-Africans (116.0 microg/kg), Asians (117.4 microg/kg) and Whites (141.2 microg/kg). Significantly different levels of total As in fingernail and urine and a higher percentage of urinary DMA in the Somali Black-Africans are suggestive of a different pattern of As metabolism in this ethnic group.     

六神丸可溶性砷形态的HPLC-ICP-MS研究

目的:建立中药复方中亚砷酸盐(AsⅢ)、砷酸盐(AsⅤ)、一甲基砷(MMA)和二甲基砷(DMA)的HPLC-ICP-MS方法。方法:采用Hamilton PRP-X100阴离子交换柱,15mmol/L(NH4)2HPO4为流动相(pH6.0),建立了同时分析中药中AsⅢ,AsⅤ、MMA和DMA的HPLC-ICP-MS方法,并对六神丸和雄黄中可溶性砷的形态进行了检测。结果:该分析方法在1~100ng/mL范围内线性关系良好,精密度和重复性良好,回收率为93%~106%。六神丸中几种药材与单味雄黄混合后,测得的可溶性砷含量均低于单味雄黄中的可溶性砷含量。蟾酥、牛黄、麝香、冰片、珍珠与雄黄混合后,砷溶出量比单味雄黄的砷溶出量依次减少93.6%,86.4%,71.3%,27.6%和14.7%。结论:六神丸复方中的几种单味药均有抑制雄黄中砷溶出的作用,推测是降低雄黄毒性作用的可能途径之一。     

地龙药材及其处方制剂散寒化湿颗粒中总砷及砷形态研究

目的 探究地龙药材至制剂过程中总砷及砷形态、价态的传递规律,以期建立地龙药材及散寒化湿颗粒（Sanhan Huashi Granules,SHG）中砷含量的限度,保障SHG的安全。方法 采用电感耦合等离子体质谱法（inductively coupledplasma mass spectrometry,ICP-MS）对经微波消解后的地龙药材到SHG进行总砷含量的测定;采用高效液相色谱-电感耦合等离子体质谱法（high performance liquid chromatography–inductively coupled plasma mass spectrometry,HPLC-ICP-MS）对其进行砷形态、价态的测定分析;并考察多批次SHG、不同产地地龙药材中砷总量以及各形态、价态的差异。结果 地龙药材、饮片、提取液及制剂在传递过程中总砷含量呈递减趋势,阴性样品中检出极少量的砷,总砷从药材至制剂的平均转移率为52.00%,饮片到制剂中的平均转移率为60.81%;28批SHG与24批地龙中砷形态及价态存在形式及规律基本一致,即基本以毒性较大的As(Ⅲ)和As(Ⅴ)为主,其他毒性较小的...