Simultaneously determination of methyl and inorganic mercury in fish species by cold vapour generation atomic absorption spectrometry

A simple and rapid non-chromatographic method was developed to determine methylmercury (MeHg) and inorganic mercury (iHg) levels in muscles tissues of 10 freshwater fish species. The MeHg and iHg were determined by cold vapour atomic absorption spectrometry after alkaline wet digestion of samples. The digested samples were reduced sequentially with stannous chloride and sodium tetrahydroborate for iHg and MeHg, respectively. Parameters such as carrier gas flow rate (argon), volume of oxidizing and potassium persulphate solutions were investigated in detail. The accuracy of the technique was evaluated by using certified reference material (DORM-2) and spiking the both Hg species in muscles tissue of a fish. The limits of detection were 0.117 and 0.133 μg kg⁻¹ for MeHg and iHg, respectively. The concentrations of MeHg and iHg in muscles tissues of ten fish species were found in the range of (28.4–56.3) and (3.01–8.11) μg kg⁻¹, respectively.     

Determination of arsenic and mercury in sunflower oil by electrothermal atomic absorption

A simple and fast method for the determination of arsenic (As) in sunflower oil by electrothermal atomic absorption (ETAAS) is described. The optimal instrumental parameters for ETAAS measurement of As species in stable and homogeneous soap emulsions prepared from oil samples with tetramethylammonium hydroxide (TMAH) have been established. The limit of determination is 5 ng g^-1 total As in sunflower oil. A second approach involving extraction of As and mercury from sunflower oil and consequent ETAAS measurement is also described. Simultaneous quantitative extraction of As(III), As(V), monomethylarsonate (MMA) and dimethylarsinate (DMA) as well as Hg(II), monomethylmercury(II)chloride (MMC), dimethylmercury (DMM), diethylmercury (DEM) and diphenylmercury (DPM) is achieved by using an extraction mixture comprising of 0.1^M NH₃/0.01^M EDTA. Pre-reduced palladium is applied as an effective modifier for the next ETAAS measurement of all extracted species. The method of standard addition is employed for calibration. The accuracy and reproducibly of the methods was established by spike and recovery experiments and parallel analysis of sunflower oils from the marketplace. Limits of determination of 2 ng g^-1 for As and 3 ng g^-1 for mercury were obtained.     

Determination of trace metals in fish species of the Ria de Aveiro (Portugal) by electrothermal atomic absorption spectrometry

Cadmium, copper, nickel, lead and zinc were determined in fish samples from seven sampling stations of the Ria de Aveiro (Portugal). The species analyzed were Anguilla anguilla, Mullus surmuletus, Trigla lucerna, Mugil cephalus, Chelon labrosus, Liza aurata and Dicentrarchus labrax, all of which are used for human consumption. For this purpose, procedures for the electrothermal atomic absorption spectrometry determination of cadmium, copper, nickel and lead in these samples were developed, as well as a microwave digestion method for obtaining a fast dissolution of the samples. The concentrations of metals found in the muscle of the fish species were very low. The minor contents corresponded to cadium, lead and nickel with values smaller than 0.043, 0.15 and 0.14 μg/g (wet weight), respectively, except in the case of nickel in the Anguilla anguilla species where more elevated concentrations were found (between 0.16 and 0.40 μg/g). The contents of copper in the samples ranged from 0.5 to 1.1 μg/g (wet wt.). Zn is the most abundant element in all fishes, with concentrations around 20 μg/g (wet wt.) in the Anguilla anguilla samples and with values oscillating between 4.7 and 12 μg/g in the rest of the species studied. In all cases, the results obtained for all the elements were considerably lower than those recommended by specific legislation for these aquatic organisms. The accuracy of the analytical methodology employed was also evaluated through the analysis of two reference materials (NIST-1577b and IAEA-V10): good agreement was obtained between the experimental results and the certified values.     

原子吸收分光光度法测定接装纸中的砷、铅

建立了用氢化物发生器-、石墨炉-原子吸收分光光度法测定接装纸中砷、铅含量的方法。结果表明:①铅测定最佳条件为样品中硝酸浓度1.0%(体积分数),添加基体改进剂;②砷测定最佳条件为样品中硝酸浓度0.05mol/L,硼氢化钠浓度2.0%(质量分数),载液中盐酸浓度5.0%(体积分数);③砷、铅的相对标准偏差≤6.65%,回收率在96.0%~103.0%之间。     

Fast determination of arsenic,selenium, nickel and vanadium in fish and shellfish by electrothermal atomic absorption spectrometry following ultrasound-assisted extraction

Ultrasound-assisted extraction of As, Se, Ni and V from fish and shellfish has been applied as a fast and reliable sample pre-treatment method for accurate determination of the four elements by electrothermal atomic absorption spectrometry with Zeeman (As, Se) or Deuterium (Ni, V) background correction. A multivariate optimization approach has been employed for establishing the effect of variables influencing the extraction process. Under suitable conditions, quantitative extractions occurred from a 10 mass sample (particle size <100 μm) suspended in 1.5 mL of acidic extractant (0.5 or 3% v/v HNO₃) and subjected to high intensity ultrasound (50% amplitude; 3 min). The method was successfully validated against the following certified reference materials: NRCC-DORM-2 dogfish muscle, NRCC-DOLT-2 dogfish liver, NRCC-TORT-2 lobster hepatopancreas, NIST-SRM 1566b oyster tissue and BCR 627 tuna fish. The following seafood samples were analyzed: hake (Merluccius merluccius), sole (Solea solea), clam (Venerupis rhomboides), prawn (Panaeus kerathurus), cuttlefish (Sepia officinalis), shrimp (Palaemon elegans), razor shell (Ensis ensis), cockle (Cardium edule), Mussel (Mytilus galloprovincialis), edible crab (Cancer pagurus), meagrin (Lepidorhombus whiffiagonis). The concentration ranges (μg/g, dry weight) for the elements determined were as follows: As (12.6–190), Se (0.73–2.34), Ni (2.94–46) and V (0.82–5.14). The detection limits (LODs), defined as 3s/m (s being the standard deviation of 10 blank and m the slope of the calibration graph), in dry tissue were 0.6, 0.3, 0.2 and 0.4 μg/g for As, Se, Ni and V, respectively. Between-batch precision was expressed as relative standard deviation from three separate extractions was in the range 3–10%.     

UV-photolysis assisted digestion of food samples for the determination of selenium by electrothermal atomic absorption spectrometry (ETAAS)

An UV-oxidation procedure has been developed to completely digest biological/food samples for the determination of trace levels of selenium. A combined use of UV photolysis and hydrogen peroxide in the presence of an oxidant (HNO₃), results in the complete oxidation of the organic matter. This method is simpler and requires fewer reagents when compared with other sample pre-treatment procedures. The clear solution obtained was analysed for the selenium content by graphite furnace atomic absorption spectrometry. Unreduced palladium-nitrate modifier was used in all cases. However, in case of samples that are known to contain sulfur (like mushroom, Brazil nut, etc.), reduced palladium was used as modifier. The method was verified using three standard reference materials i.e., Whole egg powder-8415, Tuna fish-IAEA 350, Oyster tissue-1566a, and the results were in agreement at 95% confidence level. By using standards addition as calibration method, accurate results were obtained for the certified reference material, the precision for the CRM’s were in the range of 3.5–8%. The characteristic mass of selenium is assessed as 10 pg. The detection limits were in the range of 35–40 ng/g.     

Determination of total arsenic, inorganic and organic arsenic species in wine

Forty-five wine samples from the south of Spain of different alcoholic strength were analysed for total arsenic and its inorganic [As(III), As(V)] and organic (monomethylarsonic acid [MMAA], dimethylarsinic acid [DMAA]) species. The As levels of the wine samples ranged from 2.1 to 14.6 µg l^-1. The possible effect of the alcoholic fermentation process on the levels of the total arsenic and arsenical species was studied. The average total arsenic levels for the different samples were very similar, without significant differences between all types of wines. In table wines and sherry, the percentages of total inorganic arsenic were 18.6 and 15.6%, with DMAA or MMAA being the predominant species, respectively. In most samples, DMAA was the most abundant species, but the total inorganic aresenic fraction was considerable, representing 25.4% of the total concentration of the element. The estimated daily intakes of total arsenic and total inorganic arsenic for average Spanish consumers were 0.78 and 0.15 µg/person day^-1, respectively. The results suggest that the consumption of these types of wines makes no significant contribution to the total and inorganic arsenic intake for normal drinkers. However, wine consumption contributes a higher arsenic intake than through consumption of beers and sherry brandies.     

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

目的建立高效液相色谱-电感耦合等离子体质谱法测定大米中无机砷的分析方法。方法采用两种前处理方法对大米中的无机砷进行提取,经高效液相色谱分离后,利用电感耦合等离子体质谱进行测定。同时对大米样品进行微波消解后测定其中的总砷,通过无机砷及有机砷的总和计算两种前处理方法的回收率,从而对前处理方法进行比较。对磷酸二氢铵、碳酸铵以及磷酸氢二铵等缓冲盐进行选择,并对p H值进行优化,确定最优的流动相条件。结果以12.5 mmol/L磷酸氢二铵作为流动相,调节流动相p H为8.5,流速为1 m L/min,可以将5种无机砷形态完全分离。对两种前处理方法进行比较,发现两种前处理方法的提取效率均大于87.5%,其中酸-热辅助提取法的提取效率相对更高。结论该方法准确、简单,适合大米中无机砷的测定。     

Non-chromatographic speciation of inorganic arsenic in mushrooms by hydride generation atomic fluorescence spectrometry

A non-chromatographic speciation method has been developed for the determination of inorganic arsenic in cultivated and wild mushroom samples from different origins. The ultrasound-assisted extraction of the toxic arsenic species As (III) and As (V) was performed for 10 min with 1 mol l⁻¹ H₃PO₄ and 0.1% (m/v) Triton X-100. After phase separation the residue was washed with 0.1% (w/v) EDTA and centrifuged. As (III) and As (V) were determined by hydride generation atomic fluorescence spectrometry. Speciation was made using proportional equations corresponding to two different measurement conditions, (i) directly feeding sample extracts diluted with HCl and (ii) after reduction with KI and ascorbic acid for 30 min. The limits of detection of the method were 6.3 and 5.0 ng g⁻¹ for As (III) and As (V), respectively. Recovery percentages varied between 91% and 108% for As (III) and from 90% to 109% for As (V) indicating that As species interconversion was avoided. As (III) concentrations from 264 to 81 μg g⁻¹ and As (V) concentrations from 246 to 59 μg g⁻¹ were found in Spanish cultivated mushrooms. For Chinese wild mushrooms As (III) varied between 624 and 117 μg g⁻¹ and As (V) from 380 to less than 5 μg g⁻¹. The accuracy of the method was checked by the determination of total As (from the sum of As (III) and As (V)) in a tomato leaves reference sample, with good agreement with the certified value.     

Comparison of electrothermal and hydride generation atomic absorption spectrometry for the determination of total arsenic in broiler chicken

The purpose of this study was to estimate total arsenic concentration in different tissues (leg, breast, liver and heart) of broiler chicken by hydride generation atomic absorption spectrometry (HGAAS) and graphite furnace atomic absorption spectrometry (GFAAS), prior to microwave assisted acid digestion. The accuracy of the techniques was evaluated by using certified reference material DORM-2. The percentage recoveries of total As were observed as 100.6% and 99.4% for HGAAS and GFAAS, respectively. The precision of the techniques, expressed as relative standard deviation, was observed as 1.71% and 4.18% for HGAAS and GFAAS measurements, respectively. The limits of detection for HGAAS and GFAAS were 0.025 μg/g and 0.052 μg/g, respectively. The concentrations of total arsenic in different tissues of broiler chicken were found in the range of 2.19–5.28, 2.15–5.22, 2.97–7.17 and 2.68–6.36 μg/g for leg, breast, liver and heart tissues, respectively. At a mean level of chicken consumption (60 g/person/day), people may ingest in the range of 72.0–85.1 μg arsenic/person/day from chicken alone.     

Determination of copper in fish feed by graphite furnace atomic absorption spectrometry using slurry sampling

The present work develops and optimizes a method to determine copper in samples of feces and fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer’s graphite tube coated internally with metallic rhodium and tungsten carbide that acts as chemical modifiers. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of copper) were 0.24 and 0.79 μg L⁻¹ for the standard feces slurries and 0.26 and 0.87 μg L⁻¹ for the standard feed slurries. The proposed method was applied in studies of absorption of copper in different fish feeds and their results proved compatible with that obtained from samples mineralized by acid digestion using microwave oven.     

Determination of mercury in fish by cold vapour atomic absorption spectrometry using an automatic mercury analyzer

The concentration of mercury in fish samples from the Atlantic coast of Ghana was determined using a simple, rapid and accurate method. A mixture of HNO₃, HClO₄ and H₂SO₄ was used for complete oxidation of organic tissue. Mercury is detected by the cold vapour atomic absorption spectrometry technique using an automatic mercury analyzer developed at the National Institute for Minamata Disease (NIMD). In total, 56 samples covering 13 species of fish were analysed for total mercury. The concentration of mercury in the edible muscle tissue of these fish ranged from 0.004 to 0.122 μg g⁻¹ wet weight. All fish species sampled had concentrations less than the WHO limit of 0.5 μg g⁻¹ wet weight. The low concentrations of mercury detected in the samples do not constitute any significant mercury exposure to the general population through fish consumption.     

The determination of lead in sugar and sweets without digestion by electrothermal atomic absorption spectrometry (ETAAS) with a rhodium chemical modifier

Reference methods for determining lead in food are usually time-consuming. This paper reports a straightforward procedure using electrothermal atomic absorption spectrometry (ETAAS), to determine lead (Pb) in fat-free sweets. Several chemical modifiers were examined and results showed that it is not necessary to digest the samples, when a rhodium (Rh) modifier was used. The samples were dissolved in nitric acid and the determination of Pb was performed by ETAAS, using Rh chemical modifier at a pyrolysis temperature of 900°C and an atomization temperature of 1500°C. No ashing step was employed and aqueous standards were used, in the range 2-10 µg l^-1. The limit of quantification was 0.095 mg kg^-1, and the accuracy of the method was verified by analysing certified reference materials.     

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。     

液相色谱-原子荧光法测定大米中4种砷形态

目的建立以0.3 mol/L硝酸为提取剂提取大米中4种砷形态(亚砷酸根AsⅢ、砷酸根AsⅤ、一甲基砷MMA和二甲基砷DMA)的液相色谱-原子荧光(liquid chromatography-atomic fluorescence spectrometry,LC-AFS)分析方法。方法在60℃条件下,超声40 min提取大米样品,上清液供LC-AFS测。比较2种提取方法对稻米中4种砷形态的提取效率,并对提取温度和提取时间等条件进行优化。结果 4种砷形态化合物的检出限为0.002~0.01μg/mL,加标回收率为89.03%~100.70%,RSD不大于4.36%(n=5)。结论此方法可以在1h时内完全分离大米样品中的四种砷形态,操作简单、灵敏,适用于大米中重金属砷的风险评估。     

原子吸收光谱法测定琐琐葡萄中的无机元素

目的用原子吸收光谱法测定琐琐葡萄中12种无机元素的含量.方法 称取5份经粉碎、干燥恒重后的琐琐葡萄样品1.0000 g置于150 ml三角烧瓶中,加入硝酸+高氯酸(4+1)混合溶液20 ml,电热板消化后,用超纯水稀释至刘度,在仪器工作条件下用3％稀硝酸做空白测定吸光度.用火焰原子吸收光谱法测定了琐琐葡萄中K、Ca、Na、Mg、Fe、Mn、Zn、Cu、Cr元素的含量,Cd、Pb、Se元素含量用石墨炉原子吸收光谱法测定.结果 原子吸收光谱法测定的线性相关系数为0.997 9 ～0.999 9,相对标准偏差在0.19％～4.55％之间.样品中的K、Ca、Na、Fe、Mn、Cu、Cd、Cr、Se含量分别为11 906.50、1 409.01、479.03、208.80、8.97、5.21、0.06、0.25、1.98 μg/g,Mg、Zn和Pb未检出.结论原子吸收光谱法检测琐琐葡萄中的无机元素具有良好的准确度和精密度;琐琐葡萄中K、Ca、Na、Fe、Se含量较高;琐琐葡萄抗炎作用可能与其中无机元素含量较高有关.     

Determination of total arsenic in soft drinks by hydride generation atomic fluorescence spectrometry

A highly sensitive and simple method has been developed for the determination of total arsenic, by continuous hydride generation and atomic fluorescence spectrometry (HGAFS), in refreshing drink samples as colas, teas and fruit juices. Samples were mixed with concentrated HCl and KI to obtain final concentrations of 2 mol l⁻¹ and 1%, respectively. These solutions were aspirated and merged with a reducing NaBH₄ 3% (m/v) solution, with sample and NaBH₄ flow rates of 12.5 and 1.5 ml min⁻¹, respectively. The hydride generated in a 170 cm reaction coil was transported to the detector with an Ar flow of 400 ml min⁻¹. The recovery values of added concentrations, from 0.1 to 0.9 ng ml⁻¹, of arsenic in colas, teas and fruit juices were 94 ± 5, 101 ± 9 and 94 ± 6, respectively, achieving variation coefficients between 0.1% and 9%, confirming the accuracy of developed procedure. Detection limit, ranged from 0.01 to 0.03 ng ml⁻¹. On comparing the direct determination with a reference procedure made after dry ashing operation it can be noticed that the direct approach provides a simplification of the handling and time consuming, achieving statistically comparative results.     

Selected arsenic species: As(III), As(V) and dimethylarsenic acid (DMAA) in Xerocomus badius fruiting bodies

The aim of the study was to determine the content of As(III), As(V) and DMAA (dimethylarsinic acid) in Xerocomus badius fruiting bodies collected from selected Polish forests from areas subjected to very low or high anthropopressure and some commercially available samples obtained from the Polish Sanitary Inspectorate. The arsenic species determination was provided by two independent HPLC–HG-AAS hyphenated systems. The results show high levels (up to 27.1, 40.5 and 88.3 mg kg⁻¹ for As(III), As(V) and DMAA, respectively) of arsenic and occurrence of different species in mushrooms collected from areas subjected to high anthropopressure and two commercially available samples. For mushroom samples collected from areas not subjected to high anthropopressure and two commercially available samples the arsenic species level was below 0.5 mg kg⁻¹ for each arsenic form. Therefore, the accumulation of arsenic by mushrooms may lead to high (toxic for humans) arsenic concentrations, and arsenic species levels should be monitored in mushroom foodstuffs.     

高效液相色谱-电感耦合等离子体质谱法测定婴幼儿谷类辅助食品中无机砷及其他砷形态

目的 建立高效液相色谱-电感耦合等离子体质谱法测定婴幼儿谷类辅助食品中无机砷及其他砷形态的分析方法。方法 婴幼儿谷类辅助食品经0.15 mol/L硝酸溶液提取后, 采用阴离子分析柱, 以不同浓度的碳酸铵溶液作为流动相进行梯度洗脱分离, 用高效液相色谱-电感耦合等离子体质谱进行定性和定量分析。 结果 建立的5种砷形态分析方法在0~100 μg/L范围内具有良好的线性关系, 相关系数r>0.999, 加标回收率在89.0%~110.0%, 相对标准偏差(relative standard deviation, RSD)<5%。婴幼儿谷类辅助食品中砷形态以无机砷为主, 在调查的样品中无机砷的含量均远低于国家食品标准的限量。结论 该方法简便、准确, 适用于婴幼儿谷类辅助食品中无机砷及其他砷形态的测定及食品安全的实际监测。     

快速消解-石墨炉原子吸收光谱法测定食品中砷含量

目的 建立快速消解-石墨炉原子吸收光谱法测定食品中砷含量的分析方法.方法 采用快速消解法消解3类食品,用石墨炉原子吸收光谱法测定砷的含量.结果 方法检出限和定量限分别为0.051 mg/kg和0.170 mg/kg.与微波消解-原子荧光法测定结果相比,2种方法测定大米和茶叶的绝对差值占算数平均值分别为7.2％、7.6％...