Survey of total arsenic and arsenic speciation in US-produced rice as a reference point for evaluating change and future trends

Rice generally contains higher levels of arsenic than most terrestrial-based foods. Studies related to dietary intake of arsenic from rice must take into account arsenic speciation due to toxicity differences in arsenic species. In this study, microwave-assisted extraction with trifluoroacetic acid was used to prepare rice samples for arsenic speciation analysis by high-performance liquid chromatography-inductively coupled plasma mass spectrometry. Fifty-three samples collected directly from the fields in four major rice-producing states in 1980 and 1981 were analysed for total and speciated arsenic and the results were compared with each other and with results for several more recently collected samples from local markets. The average content of total arsenic was 210 ± 190 ng As g^?1. This study demonstrates that US rice samples with higher levels of total arsenic have higher levels of dimethylarsinic acid; however, inorganic arsenic levels, regardless of the total arsenic content, rarely exceed 150 ng As g^?1 dry weight. These data are consistent with more recent findings, thus establishing trends that arsenic content in US-grown rice has been relatively constant throughout the last 30 years. To the authors’ knowledge, the presented data are unique in that they provide a historical reference point for arsenic distribution in US-produced rice. These data would be invaluable for several applications including long-term arsenic exposure studies, environmental clean-up assessments, and to establish models for future trends in arsenic contribution in total diet studies.     

Total arsenic in rice milk

Rice milk and its by-products were tested for total arsenic concentration. Total arsenic concentration was determined using graphite-furnace atomic absorption spectrometry. The arsenic concentrations ranged from 2.7 ± 0.3 to 17.9 ± 0.5 µg L^?1. Rice milk and its by-products are not clearly defined as food, water or milk substitute. The US Environmental Protection Agency (EPA), the European Union (EU) and the World Health Organization (WHO) have set a level of 10 µg L^?1 for total arsenic concentrations in drinking water. The EU and the US regulatory agencies do not provide any guidelines on total arsenic concentrations in foods. This study provides us with a starting point to address this issue in the State of Mississippi, USA.     

高效液相色谱-电感耦合等离子体质谱法测定大米中无机砷

摘要：目的 建立高效液相串联电感耦合等离子体质谱法测定大米中无机砷的分析方法。方法 样品经0.15mol/L硝酸溶液提取,以100 mmol/L (NH4)2CO3为流动相,使用AS7 阴离子交换柱(250 mm×4.0 mm, 10 μm)分离,进入质谱进行检测。结果 As（Ⅲ）和As（Ⅴ）在浓度0~100ng/mL范围内线性相关性良好,精密度RSD均小于5%,检出限为0.234ng/mL~0.904ng/mL,加标回收率在89.7%~108.0%之间,能力验证和质控样结果较好。结论 此方法适用于大米中无机砷的快速检测。     

Elements in rice from the Swedish market: 1. Cadmium, lead and arsenic (total and inorganic)

A survey of the levels of cadmium, lead and arsenic in different types of rice available on the Swedish retail market was carried out in 2001-03. The types of rice included long and short grain, brown, white, and parboiled white rice. The mean levels found were as follows: total As: 0.20 mg kg^-1, inorganic As: 0.11 mg kg^-1; Cd: 0.024 mg kg^-1; and Pb: 0.004 mg kg^-1. ICP-MS was used for the determination of As (total and inorganic) after acid digestion. Lead and cadmium were determined using graphite furnace atomic absorption spectrometry (GFAAS) after dry ashing. In countries where rice is a staple food, it may represent a significant contribution in relation to the provisional tolerable weekly intake for Cd and inorganic As.     

Elements in rice from the Swedish market: 1. Cadmium,lead and arsenic (total and inorganic)

A survey of the levels of cadmium, lead and arsenic in different types of rice available on the Swedish retail market was carried out in 2001–03. The types of rice included long and short grain, brown, white, and parboiled white rice. The mean levels found were as follows: total As: 0.20 mg kg^?1, inorganic As: 0.11 mg kg^?1; Cd: 0.024 mg kg^?1; and Pb: 0.004 mg kg^?1. ICP-MS was used for the determination of As (total and inorganic) after acid digestion. Lead and cadmium were determined using graphite furnace atomic absorption spectrometry (GFAAS) after dry ashing. In countries where rice is a staple food, it may represent a significant contribution in relation to the provisional tolerable weekly intake for Cd and inorganic As.     

炭黑氨基柱净化HPLC-ICP-MS测定黄酒中砷形态及含量

建立了一种同时测定黄酒中亚砷酸根、砷酸根、砷甜菜碱、一甲基砷酸和二甲基砷酸等5种砷形态的高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)分析方法。黄酒经炭黑氨基柱净化,体积分数为10%甲醇水溶液洗脱,采用Hamilton PRP-XIO0阴离子交换色谱柱(4.1 mm×250 mm,10 μm),60 mmol/L硝酸铵梯度洗脱,高效液相色谱分离,电感耦合等离子体质谱进行定性和定量分析。在0.5～20.0 μg/L范围内各砷形态线性良好,相关系数R均＞0.999;加标回收率85%～92%,相对标准偏差(RSD)1.4%～5.2%;5种砷形态的定量限均为0.10 μg/L,检出限均为0.03 μg/L。利用该方法对不同年份、不同企业及不同类型的黄酒进行了检测,该方法适用于黄酒中砷残留的分析检测。     

Dietary intake of arsenic by children and adults from Jinhu area of China

The aim of this study was to estimate the dietary intake of arsenic (As) by children and adults from Jinhu area of China. A duplicate diet approach was used to collect diet samples in November and December 2007. The As content was measured by hydride generation atomic fluorescence spectrometry. The As intakes (median) for different group were: children: 0.6 µg kg^?1 bw day^?1 or 6.7 µg kg^?1 bw week^?1; adults: 0.5 µg kg ^?1 bw day^?1 or 3.8 µg kg ^?1 bw week^?1, none of which exceeded the provisional tolerable weekly intake (PTWI) of 15 µg kg ^?1 bw week^?1 for As proposed by the World Health Organization (WHO). The median and maximum of the children group amounted to 44.7% and 125.3% of the PTWI; the values for adults were 25.3% and 118.7%, respectively. There were 3.3% of children whose weekly As intake exceeded the PTWI, and there were 6.7% of adults whose weekly As intake exceeded the PTWI. It is concluded that dietary As intake was safe for most people in Jinhu area, but the high dietary As intake for a minority of people in this area deserves attention.     

粳稻谷中总砷和无机砷含量的测定及分布情况

本文采用ICP-MS法和LC-AFS法分别测定粳稻谷中的总砷和无机砷含量.结果表明:总砷在0?10 ng/mL的浓度范围内呈良好的线性关系,检出限为0.020 7 ng/mL;As3+和As5+在0?50 ng/mL的浓度范围内呈良好的线性关系,As3+检出限为0.24 ng/mL,As5+检出限为0.44 ng/mL...     

稻米中总砷及无机砷含量的测定与分析

采用氢化物原子荧光光度法测定13份稻米样品中的总砷和无机砷含量,结果表明：所测稻米样品中均检出总砷与无机砷,总砷含量范围为0.06~0.20 mg/kg,无机砷含量范围为0.039~0.150 mg/kg,无机砷占总砷的含量为50.0%~93.1%,无机砷含量在国家限量卫生标准以内;未冲洗大米样品中总砷含量仅为糙米的72.7%~90.0%,无机砷含量为糙米的62.7%~87.7%;多次冲洗的大米样品中总砷含量仅为未冲洗大米的75.0%~91.7%,无机砷含量为83.0%~93.6%。提高加工精度和用水淘洗均能在一定程度上降低总砷与无机砷的含量,减轻人们食用后对身体的危害。     

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%).     

Rapid sample preparation procedure for As speciation in food samples by LC-ICP-MS

This paper describes a rapid method for arsenic (As) speciation by LC-ICP-MS in several types of food samples. Prior to analysis, samples were milled and the As species extracted from biological tissues by sonication in only 2?min with a solution containing MeOH (10%, v/v) plus HNO₃ (2%, v/v). As species were separated by LC using an anion exchange column. Method detection limits for AsB, As³⁺, DMA, MMA and As⁵⁺ were 1.3, 0.9, 0.6, 0.7 and 0.8?ng?g^?1, respectively. Method accuracy and precision were traceable to Certified Reference Materials SRM1577 bovine liver from the National Institute of Standards and Technology, CE278 mussel tissue from the Institute of Reference Materials and Measurements and DOLT-3 dogfish liver tissue and DORM-3 fish protein from the National Research Council of Canada. Finally, the method was applied to speciate As in food samples (egg, fish muscle, beef and chicken) purchased in Brazilian markets.     

Dietary exposure to metals and other elements in the 2006 UK Total Diet Study and some trends over the last 30 years

Concentrations of 24 elements including metals in the 2006 UK Total Diet Study (TDS) were measured and dietary exposures estimated. Composite samples for the 20 TDS food groups (bread, fish, fruit, etc.) were collected from 24 UK towns and analysed for their levels of aluminium, antimony, arsenic, barium, bismuth, cadmium, chromium, copper, germanium, indium, lead, manganese, mercury, molybdenum, nickel, palladium, platinum, rhodium, ruthenium, selenium, strontium, thallium, tin, and zinc. Concentrations of each of the elements in the food groups were lower than or similar to those reported in the previous TDS survey, conducted in 2000, with the exception of aluminium, barium, and manganese. Dietary exposures to the 24 elements were estimated for UK consumers and compared with previous estimates made over the last 30 years in order to examine any trends in exposure to these elements in the typical UK diet. Population exposures to the elements have generally declined over time, and exposures to most of these elements remain at low levels. The independent UK Government scientific Committee on Toxicity of Chemicals in Food, Consumer Products and the Environment (COT) commented on the estimated dietary exposures, taking into account their previous evaluations (in 2003 and 2008), and identified no major concerns for the health of consumers, but did advise that there was a need for more information on aluminium and barium, and also commented that dietary exposure to inorganic arsenic and to lead should continue to be reduced.     

云南省不同产地大米重金属砷污染风险分析

目的分析云南省不同产地大米重金属砷的污染风险。方法采用LC-AFS6500型原子荧光光度计,分析采集自云南省16个州(市)水稻主要产区的118个县(市/区)2592份稻谷的无机砷含量,并进行相关性分析、方差分析和LSD多重比较。结果供试样品无机砷含量的平均值为0.028 mg/kg,其中,工矿企业周边农田(0.036 mg/kg)一般农田(0.026 mg/kg)污水灌溉农田(0.021 mg/kg),以工矿企业周边农田重金属砷污染风险最大,经方差分析,F值为16.994,呈极显著差异。工矿企业周边农田和污水灌溉农田无机砷含量均以红河州为最高,分别为0.128、0.055 mg/kg,一般农田则以丽江市为最高,为0.078 mg/kg,且均与其他所有州(市)均呈极显著差异;普洱市的无机砷均值在16个州(市)中为最小,检出率最低;2592个样品中,有13份样品无机砷含量超限,占供试样品的0.50%,均采自红河州,其中个旧市6份、蒙自市5份和开远市2份。结论农业生态环境是影响大米重金属砷污染的重要因素,建议应对工矿企业周边农田重金属砷污染给予重点关注。     

Effect of cooking method and rice type on arsenic concentration in cooked rice and the estimation of arsenic dietary intake in a rural village in West Bengal,India

Arsenic (As) contamination of rice plants can result in high total As concentrations (t-As) in cooked rice, especially if As-contaminated water is used for cooking. This study examines two variables: (1) the cooking method (water volume and inclusion of a washing step); and (2) the rice type (atab and boiled). Cooking water and raw atab and boiled rice contained 40 μg As l^?1 and 185 and 315 μg As kg^?1, respectively. In general, all cooking methods increased t-As from the levels in raw rice; however, raw boiled rice decreased its t-As by 12.7% when cooked by the traditional method, but increased by 15.9% or 23.5% when cooked by the intermediate or contemporary methods, respectively. Based on the best possible scenario (the traditional cooking method leading to the lowest level of contamination, and the atab rice type with the lowest As content), t-As daily intake was estimated to be 328 μg, which was twice the tolerable daily intake of 150 μg.     

原子荧光光谱法测定糙米粉中总砷及无机砷的含量

目的 建立原子荧光光谱法测定糙米粉中总砷及无机砷含量的分析方法。方法 糙米粉经烘干称取后, 用硝酸高氯酸硫酸混合湿法消解快速进行总砷前处理, 用1%硝酸水浴热提取进行无机砷前处理, 分别利用原子荧光光谱法及液相色谱-原子荧光光谱法进行总砷和无机砷的测定。结果 总砷在6.0~20.0 μg/L浓度范围内, 无机砷在10.0~100.0 μg/L浓度范围内均具有良好的线性关系(r＞0.999), 大米粉质控样测定值总砷0.26 mg/kg及无机砷0.17 mg/kg, 均在参考值允许范围内, 回收率范围为92.3%~127.1%, 均具有较高的回收率。结论 优化湿法消解处理能较高效地得到准确的测定结果, 糙米粉中无机砷经热提取及流动相环节的优化后, 也可得满意检测结果。     

粳稻谷中镉和无机砷分布探讨

通过对糙米和大米中镉和无机砷含量的分析,发现镉在粳稻谷中分布较均匀,其含量在糙米和大米中基本一致;而无机砷在粳稻谷中主要分布在表皮,糙米通过精加工碾磨成大米后,其无机砷含量约降低了2倍。为去除粮食中重金属残留,实现粮食资源的合理化应用提供依据。     

Determination of the Metals by ICP-MS in Wild Mushrooms from Yunnan, China

The elemental contents of Li, Cs, U, Co, As, Sr, Cd, Ba, Pb, Sb in 157 wild-grown mushrooms were determined by inductively coupled plasma mass spectrometry (ICP-MS). The mushrooms including 9 species were collected from 5 counties in Yunnan province, China. Based on the findings for the results from the certified reference materials GBW10014 (cabbage) and GBW10016 (tea), the data from the sample mushrooms were corrected. The contents of investigated trace elements in mushroom samples were determined as μg/g dry weight (dw) in the range of 0.030 to 13 for Li, 0.070 to 8.1 for Cs, 0.0010 to 0.28 for U, 0.040 to 5.4 for Co, 0.070 to 44 for As, 0.28 to 86 for Sr, and 0.15 to 23 for Cd. The maximum contents were 58, 11, and 0.11 for Ba, Pb, and Sb, respectively. The minimum contents of Ba, Pb, and Sb were below the detection limit of the method used. Practical Application: The analysis of 9 species wild-grown edible mushrooms in different regions provides the useful information to evaluate the levels of elements or of the toxic heavy metals, such as Cd, As in wild-grown edible mushrooms which grew in different regions of China for consumers and other interested groups, especially for the regulators.     

2001—2017年我国部分地区蔬菜中砷和重金属累积特征及膳食暴露风险

目的 探讨我国部分地区蔬菜中砷和重金属的累积特征,并分析潜在膳食暴露风险。方法 搜索论文数据库,收集2001—2017年发表文献中蔬菜铜(Cu)、铅(Pb)、镉(Cd)、铬(Cr)、砷(As)及汞(Hg)含量的数据,分析我国根茎类、叶菜类及茄果类蔬菜中As和重金属的污染特性,并采用美国环保署推荐的健康风险评价模型评估蔬菜中砷和重金属的膳食暴露风险。结果 3类蔬菜中Cu、Pb、Cd、Cr、As和Hg均呈非正态分布,变异系数均<10%。根茎类、叶菜类及茄果类蔬菜中Cd、As、Hg的含量均差异有统计学意义(P<0.05),叶菜类和茄果类蔬菜中Pb-Cr含量差异有统计学意义(P<0.05),但3类蔬菜中Cu含量均差异无统计学意义(P>0.05)。根茎类蔬菜中Pb、As和Hg的含量较高,叶菜类蔬菜中Cd含量较高。根茎类和叶菜类蔬菜中Pb-Cd及根茎类蔬菜中Pb-Cr相关性均较强(P<0.01)。3类蔬菜中Cu、Cd、Cr和As污染指数均在安全范围内,而根茎类和叶菜类蔬菜中的Pb和Hg均存在不同程度的污染,但基本属于轻度污染。根茎类和茄果类数值中As和重金属对成人和儿童的风险值均<1.0,但叶菜类蔬菜中Pb对成人和儿童的风险值的第95百分位数分别是1.780和2.020,表明叶菜类蔬菜中的Pb存在潜在的人体非致癌风险。结论 中国蔬菜中Cu、Cd、Cr、As和Hg整体污染较轻,但叶菜类蔬菜中Pb污染应引起重视。     

苏州市场大米中重金属铅、镉、铬含量比较

大米是人类赖以生存的主食之一,随着工业化进程的加快,稻米种植土壤的重金属污染越来越严重,该文对苏州市场中产区分别为华东和东北地区的37个大米样品进行了重金属铅(Pb)、镉(Cd)、铬(Cr)的分析。实验结果证实东北产区的大米的铅、镉含量跟华东地区的比在均值的95%置信区间具有显著差异,而铬含量无显著差异。东北地区产的大米的平均铅、镉含量比华东地区的低。