Nitric acid-based partial-digestion method for selective determination of inorganic arsenic in hijiki and application to soaked hijiki

Because there is a great difference between the toxicity of inorganic arsenic (As) and organic As in food, the JECFA has set a PTWI value for inorganic As (iAs) rather than for total As. The difference in As toxicity makes it necessary to extract iAs completely from food samples for toxicological analysis, but complete extraction of As from most foods including seaweed has not been achieved to date. We developed a partial-digestion method that uses nitric acid as a solvent in order to extract almost all arsenicals from the solid matrix of hijiki (Hizikia fusiforme, a brown alga) samples. In this method, organic As species were not converted into iAs. HPLC/ICP-MS was then used to determine the concentration of iAs. Total As was measured by hydride generation-atomic absorption spectrometry. The adopted conditions for 0.1 g of ground fine powder sample were: 2 mL of 0.3 mol/L nitric acid; heating, 80 degrees C for 1 hr. Intra-laboratory validation of the method showed good precision and accuracy. The repeatability and intermediate precision for iAs were 1.5% and 1.5%, respectively. The LOD and LOQ for iAs were 0.14 and 0.46 mg/kg dry weight, respectively. Recovery studies performed by spiking 0.5 mg/kg dry weight as the LOQ level and by spiking 3 mg/kg dry weight as the iAs concentration of an un-spiked hijiki sample showed good accuracy. The method was applied to hijiki samples after a water soaking process and a water soaking and simmering process. The results suggested that the As concentration in hijiki after both processes was lower than that before the treatments and that the water soaking and simmering process reduced the iAs concentration much more effectively than the water soaking process.     

超标稻米打磨降镉技术及工艺参数优化研究

针对湖南地区镉含量0.1~0.6 mg/kg区间的9个籼稻品种稻米,采用现有的精米机械进行打磨降镉实验。结果显示,打磨度在19%以下时,降镉效率高,对整米率的影响较小,现有精米机械打磨是镉超标糙米的有效降镉技术途径;单位米粒流量、单次打磨度、单位减重效率等最佳工艺参数组合,短粒型分别为11.6 kg/min/L、3.3和363.0 g/min/L,长粒型的分别为11.0 kg/min/L、2.3和226.4 g/min/L。但是,要将所有稻米品种的镉含量从0.6 mg/kg降至0.2 mg/kg水平以下,现有精米机械存在一定的局限性。     

Inorganic arsenic in rice bran and its products are an order of magnitude higher than in bulk grain

Rice is more elevated in arsenic than all other grain crops tested to date, with whole grain (brown) rice having higher arsenic levels than polished (white). It is reported here that rice bran, both commercially purchased and specifically milled for this study, have levels of inorganic arsenic, a nonthreshold, class 1 carcinogen, reaching concentrations of approximately 1 mg/kg dry weight, around 10-20 fold higher than concentrations found in bulk grain. Although pure rice bran is used as a health food supplement, perhaps of more concern is rice bran solubles, which are marketed as a superfood and as a supplement to malnourished children in international aid programs. Five rice bran solubles products were tested, sourced from the United States and Japan, and were found to have 0.61-1.9 mg/kg inorganic arsenic. Manufactures recommend approximately 20 g servings of the rice bran solubles per day, which equates to a 0.012-0.038 mg intake of inorganic arsenic. There are no maximum concentration levels (MCLs) set for arsenic or its species in food stuffs. EU and U.S. water regulations, set at 0.01 mg/L total or inorganic arsenic, respectively, are based on the assumption that 1 L of water per day is consumed, i.e., 0.01 mg of arsenic/ day. At the manufacturers recommended rice bran solubles consumption rate, inorganic arsenic intake exceeds 0.01 mg/ day, remembering that rice bran solubles are targeted at malnourished children and that actual risk is based on mg kg(-1) day(-1) intake.     

Arsenic accumulation and metabolism in rice (Oryza sativa L.)

The use of arsenic (As) contaminated groundwater for irrigation of crops has resulted in elevated concentrations of arsenic in agricultural soils in Bangladesh, West Bengal (India), and elsewhere. Paddy rice (Oryza sativa L.) is the main agricultural crop grown in the arsenic-affected areas of Bangladesh. There is, therefore, concern regarding accumulation of arsenic in rice grown those soils. A greenhouse study was conducted to examine the effects of arsenic-contaminated irrigation water on the growth of rice and uptake and speciation of arsenic. Treatments of the greenhouse experiment consisted of two phosphate doses and seven different arsenate concentrations ranging from 0 to 8 mg of As L(-1) applied regularly throughout the 170-day post-transplantation growing period until plants were ready for harvesting. Increasing the concentration of arsenate in irrigation water significantly decreased plant height, grain yield, the number of filled grains, grain weight, and root biomass, while the arsenic concentrations in root, straw, and rice husk increased significantly. Concentrations of arsenic in rice grain did not exceed the food hygiene concentration limit (1.0 mg of As kg(-1) dry weight). The concentrations of arsenic in rice straw (up to 91.8 mg kg(-1) for the highest As treatment) were of the same order of magnitude as root arsenic concentrations (up to 107.5 mg kg(-1)), suggesting that arsenic can be readily translocated to the shoot. While not covered by food hygiene regulations, rice straw is used as cattle feed in many countries including Bangladesh. The high arsenic concentrations may have the potential for adverse health effects on the cattle and an increase of arsenic exposure in humans via the plant-animal-human pathway. Arsenic concentrations in rice plant parts except husk were not affected by application of phosphate. As the concentration of arsenic in the rice grain was low, arsenic speciation was performed only on rice straw to predict the risk associated with feeding contaminated straw to the cattle. Speciation of arsenic in tissues (using HPLC-ICP-MS) revealed that the predominant species present in straw was arsenate followed by arsenite and dimethylarsinic acid (DMAA). As DMAA is only present at low concentrations, it is unlikely this will greatly alter the toxicity of arsenic present in rice.     

区域性稻谷采样方案的优化

污染物监测调查工作的基础前提是采样,为探索稻谷中重金属污染调查的最佳采样量和布点方法,对研究区域内稻谷中重金属,总As、iAs、Cd、总Hg、Pb的含量进行采样分析,并利用经典统计学和分层抽样技术对该区域水稻中重金属的空间变异性和合理采样方案进行了研究。结果表明：研究区域糙米中6种重金属含量均呈对数正态分布,且平均值均低于国家限量。采用半方差函数拟合,总As、iAs、Cd、Pb均符合高斯模型,且决定系数均达到0.815以上,呈现中等或以上程度的空间相关性。比较经典统计学和分层抽样两种方法,得出以土壤类型对应的稻谷种植面积分层方法可减少约46.6%的采样数量,大幅降低采样及分析成本。以半方差函数拟合情况作为最优样点布局准则,得出最优采样布局,经描述性统计、概率分布和半方差函数等验证采样方案对于研究区域糙米中总As、iAs、Cd、Pb元素的适应性。     

糙米发芽的制备技术研究

以重庆主要种植的稻米为试材,研究了其糙米制备发芽糙米的工艺技术和主要成分变化。结果表明,制备发芽糙米的最适稻米品种为丰优香粘,其最适工艺技术条件为浸泡温度30℃、浸泡时间15 h、发芽温度35℃、发芽时间25 h;发芽糙米中淀粉含量低于精白米和糙米,还原糖、蛋白质、γ-氨基丁酸和游离氨基酸含量均高于精白米和糙米。     

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.     

主要重金属在污染稻谷籽粒中的分布规律研究

以湖南省稻谷为研究对象,检测分析稻谷籽粒的稻壳、糠粉、糙米、精米等加工产品中无机As、Cd、Pb、Hg 4种重金属的变化分布规律,并研究了当前稻谷加工工艺对主要重金属的脱除效果。结果表明:无机As、Cd、Pd、Hg 4种重金属均表现出糠粉中的含量显著高于其他部位的含量。碾米加工工艺可同时消减稻谷中4种重金属的含量,其中无机As消减效果最好,消减幅度可达39%。无机As、Cd、Pb、Hg在精米与糙米中的含量均成正比,其比值分别为0.61、0.93、0.83、0.93。通过该比值关系,可通过碾米工艺获得重金属含量达标的稻谷无机As、Cd、Pb、Hg的限量值分别为0.328、0.215、0.241、0.021 5 mg/kg。     

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。     

Arsenic species in rice and rice-based products consumed by toddlers in Switzerland

Inorganic arsenic (iAs) is a contaminant present in food, especially in rice and rice-based products. Toxicity of arsenic compounds (As) depends on species and oxidative state. iAs species, such as arsenite (As(III)) and arsenate (As(V)), are more bioactive and toxic than organic arsenic species, like methylarsonic acid (MMA(V)) and dimethylarsinic acid (DMA(V)) or arsenosugars and arsenobetaine. An ion chromatography-inductively coupled-plasma-mass spectroscopy method was developed to separate the four following arsenic anions: As(III), As(V), MMA(V) and DMA(V). Sample preparation was done in mild acidic conditions to ensure species preservation. The predominant arsenic species found in rice and rice-based products, except for rice drinks, was As(III), with 60–80% of the total As content, followed by DMA(V) and As(V). MMA(V) was measured only at low levels (<3%). Analyses of rice products (N = 105) intended for toddlers, including special products destined for infants and toddlers, such as dry form baby foods (N = 12) or ready-to-use form (N = 9), were done. It was found in this study that there is little or no margin of exposure. Risk assessment, using the occurrence data and indicated intake scenarios compared to reference BMDLs as established by EFSA, demonstrated toddlers with a high consumption of rice based cereals and rice drinks are at risk of high iAs exposure, for which a potential health risk cannot be excluded.     

食物慢性砷暴露对小鼠脑组织中砷形态的影响

为探索食物慢性砷暴露对生物体脑组织的影响,本研究以水稻中的砷形态和比例为参考,设计了三个含砷剂量组:模拟组(S):0.91 mg/kg;低剂量组(L):9.10 mg/kg;高剂量组(H):30 mg/kg,对C57BL/6小鼠进行为期三个月的染毒研究,并测定小鼠血和脑组织中总砷和各种砷形态(i AsIII、i AsV、MMA、DMA和As B)的含量。结果显示,在C、S、L和H中,血的总砷含量分别为0.022、0.023、0.068和0.132 mg/kg;大脑的总砷含量分别为0、0.006、0.075和0.172 mg/kg;其中,五种砷形态均可在血液中检测到,在L、H组小鼠大脑中仅检测到DMA和未知形态的砷(u As)。因此,小鼠血液和大脑中的总砷含量随暴露剂量增大而升高,砷在体内的解毒过程也随暴露剂量增大而加速;血液中有机砷与无机砷之比可反映机体砷暴露水平;尽管食物中无机砷不能通过血脑屏障,但由于大脑中仍能检测到低毒的DMA和毒性未知的u As,因此,食物的砷毒特别是大米的砷毒性仍应引起关注。     

Di(2-ethylhexyl) phthalate contamination of retail packed lunches caused by PVC gloves used in the preparation of foods

Plasticizer contamination of foods sold in retail packed lunches and set lunches in restaurants was determined by GC/MS. The phthalate esters were as follows: diethyl, dipropyl, dibutyl, dipentyl, dihexyl, butylbenzyl, dicyclohexyl, di(2-ethylhexyl), dioctyl, diisooctyl (mixture of isomers) and diisononyl (mixture). Di(2- ethylhexyl) adipate was also determined. Sixteen packed lunches and ten set lunches were analysed, and in all samples the concentration of di(2-ethylhexyl) phthalate (DEHP) was the highest, at 0.80-11.8 mg/ kg in packed lunches and 0.012-0.30 mg/kg in set lunches. The DEHP content of five packed lunches exceeded 1.85 mg, which is the EU tolerable daily intake (TDI) for a person of 50 kg body weight. Foodstuffs that were components of the packed lunches were taken from the factory at each step of preparation and phthalates were determined. For example, chicken contained 0.08 mg/kg DEHP when uncooked, 13.1 mg/ kg after frying and 16.9 mg/kg after packing. Disposable PVC gloves used in the preparation of foods were apparently the source of high DEHP concentrations. The gloves used during cooking or packaging were sprayed with 68% (w/w) ethanol to sterilize them. PVC gloves from the factory contained 22 or 41% by weight of DEHP. To confirm the link with the contamination problem, samples of boiled rice, croquette and boiled dry radish were handled in the laboratory with PVC gloves containing 30% (w/w) DEHP. DEHP migration levels of 0.05 mg/kg in rice or 0.33 mg/kg in croquette, and 11.1 mg/kg in radish were found. The alcohol sprayed onto the gloves increased the migration of DEHP to 2.03 mg/kg in rice, 2.45 mg/ kg in croquette, and 18.4 mg/kg in radish.     

Total and inorganic arsenic in foods of the first Hong Kong total diet study

Arsenic (As) is a metalloid that occurs in different inorganic and organic forms, which are found in the environment from both natural occurrence and anthropogenic activity. The inorganic forms of As (iAs) are more toxic as compared with the organic As, but so far most of the occurrence data in food collected in the framework of official food control are still reported as total As without differentiating the various As species. In this paper, total As and iAs contents of 600 total diet study (TDS) samples, subdivided into 15 different food groups, were quantified by high-resolution inductively coupled plasma mass spectrometry (HR-ICP/MS) and hydride generation (HG) ICP/MS respectively. The method detection limits for both total As and iAs were 3 μg As kg^?1. As the samples were prepared for TDS, food items were purchased directly from the market or prepared as for normal consumption, i.e. table ready, in the manner most representative of and consistent with cultural habits in Hong Kong as far as practicable. The highest total As and iAs content were found in ‘fish, seafood and their products’ and ‘vegetables and their products’ respectively. Besides, this paper also presents the ratios of iAs and total As content in different ready-to-eat food items. The highest ratio of iAs to total As was found in ‘vegetables and their products’. It is likely that iAs in vegetables maintained its status even after cooking.     

应用近红外光谱技术快速测定粳稻品种的直链淀粉含量

应用近红外光谱法以稻谷、糙米、精米、糙米粉和精米粉为扫描材料分别建立了粳稻直链淀粉含量的预测模型。结果表明采用光谱预处理的校正效果比不采用预处理的好,用偏最小二乘法(PLS)获得的粳稻稻谷、糙米、精米、糙米粉、精米粉的回归模型和交叉验证结果为:最优校正决定系数(R2)和交叉检验均方误差(RMSECV)分别为0.8136、2.74,0.8864、2.56,0.8915、2.59,0.9261、2.26,0.9505、1.83,粉碎性样品的误差比整粒样品的误差小。育种实践中,低世代可选用糙米、高世代可选用糙米粉或精米粉作为扫描样本测定稻米直链淀粉含量。     

UPLC-MS/MS法测定糙米和稻壳中吡唑醚菌酯残留

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)法测定糙米和稻壳中吡唑醚菌酯残留的方法。样品中吡唑醚菌酯经乙腈水溶液提取、弗罗里硅土柱净化后,以C_(18)反相柱为分析柱,甲酸水溶液-甲醇为流动相,在多反应监测模式下进行质谱检测,采用电喷雾正离子源,外标法定量。吡唑醚菌酯在0.02~0.50 mg/L范围内与峰面积呈良好线性关系,线性方程为:y=77425 x+630.82,相关系数的平方为0.9979。向空白糙米、空白稻壳中分别添加吡唑醚菌酯标样,使其添加量分别为0.02、0.05、0.10 mg/kg时,平均回收率分别为84.7%~101.0%和86.2%~102.5%,相对标准偏差分别为3.7%~4.9%和5.8%~8.1%。糙米和稻壳中吡唑醚菌酯的最低检测限均为0.2μg/kg。该方法的灵敏度和准确度都较高,适合于糙米和稻壳中吡唑醚菌酯的残留分析。     

低温挤压对粳糙米营养特性及理化性质的影响

为了保留糙米的营养成分,改善糙米的粗糙口感,降低挤压糙米的消化速度,本文将粳糙米粉碎后在较低温度下挤压重组成米粒产品。将粳糙米在65 ℃低温挤压后,分析其营养成分、热特性、糊化特性、水合性质以及晶体结构等理化性质的变化。结果表明:低温挤压处理后粳糙米的脂肪含量从3.30%下降到1.07%,总淀粉、粗蛋白含量变化不显著,总膳食纤维含量从4.27%减少至3.60%,有助于改善糙米的粗糙口感。总酚含量和γ-氨基丁酸含量分别从33.99 mg/100 g、94.79 mg/kg增至36.59 mg/100 g、105.44 mg/kg。挤压后粳糙米粉的峰值黏度、回生值、糊化焓变分别由920.00 cP、869.50 cP、7.00 J/g降至406.00 cP、714.50 cP、2.28 J/g,糊化度为68.43%,挤压后糙米淀粉保持较低的糊化度。晶体结构在挤压后也发生了变化,挤压后粳糙米在2θ角为13 °、20 °存在衍射峰,晶体结构从A型转变成V型,相对结晶度从37.52%降至27.33%。此外,挤压粳糙米的吸水性指数和水溶性指数均升高。     

富硒发芽糙米生产工艺的优化

目的：研究富硒发芽糙米的最佳生产工艺。方法：通过单因素试验及Box-Behnken 组合设计考察浸泡液中亚硒酸钠质量浓度、发芽时间、发芽温度以及它们之间的交互作用对糙米发芽率及重要营养物质γ- 氨基丁酸含量的影响,通过软件分析得到使发芽率及γ- 氨基丁酸含量均达到最大值的最佳生产工艺。结果：建立富硒发芽糙米发芽率与γ- 氨基丁酸含量的数学模型,富硒发芽糙米的最佳工艺参数为：浸泡液中亚硒酸钠质量浓度5mg/L,浸泡时间9h,浸泡温度28℃,培养时间21h,培养温度31.5℃。该条件下得到发芽率77.67%,GABA 含量330mg/kg,硒含量0.5mg/kg 的富硒发芽糙米。     

糙米调质前后大米食用品质的研究

本文以超声波雾化方式对低水分粳型糙米进行调质，探讨调质对大米食用品质的变化影响。研究结果表明，采用碱性水对糙米调质后大米的食用品质得到一定的改善，大米淀粉的初始糊化温度有所降低，米汤的pH值有所提高，米饭的黏度／硬度比提高了8．8％，米饭的感官评分比未调质的样品上升了5．4％。另一方面，米糠的游离脂肪酸值也发生了较大的变化，使用碱性水调质的米糠比未调质米糠游离脂肪酸值降低23．5％，一定程度上抑制了米糠的酸败，有利于米糠的保鲜和综合利用。     

Elements in rice on the Swedish market: part 2. Chromium, copper, iron, manganese, platinum, rubidium, selenium and zinc

A survey of the levels of some essential and non-essential trace elements 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. The mean levels found were: chromium (Cr) = 0.008 mg kg(-1), copper (Cu) = 1.9 mg kg(-1), iron (Fe) = 4.7 mg kg(-1), manganese (Mn) = 16 mg kg(-1), platinum (Pt) < 0.0003 mg kg(-1), rubidium (Rb) = 3.3 mg kg(-1), selenium (Se) =0.1 mg kg(-1); and zinc (Zn) = 15 mg kg(-1). Inductively coupled plasma-mass spectrometry (ICP-MS) was used for the determination of Pt, Rb, and Se, after acid digestion. All other elements were determined using atomic absorption spectrometry (AAS) after dry ashing. Intake calculations were performed and it was concluded that rice may contribute considerably to the daily requirements of the essential elements Cu, Fe, Mn, Se, and Zn if rice consumption is high. The levels of some elements, e.g. Fe and Mn, were significantly higher in brown compared with white rice.     

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。