Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.     

苯并(a)芘在四种食用淡水鱼中的含量和分布

利用GC-MS测定了购自北京市场的4种食用淡水鱼(鲫鱼、胖头鱼、鲤鱼、草鱼)的5种组织器官(脑、肝、泡、卵和肌肉)中BaP的含量,分析了BaP在4种食用淡水鱼中的分布特征及其对人体的健康风险.结果表明,鱼体BaP湿重含量范围为0～0.057ng·g-1,BaP脂标化含量范围为0.02～21·22 ng˙g-1·BaP在不同组织器官和不同鱼种中的湿重含量差别不显著;而不同鱼种和组织器官中BaP脂标化含量则有一定的差异性.4种鱼中,胖头鱼BaP脂标化含量水平最高,鲫鱼次之,草鱼和鲤鱼较低;各组织器官中,肝脏的BaP脂标化含量相对最高,肉、泡、籽次之,脑中BaP脂标化含量相对最低.鱼体中BaP湿重含量均低于USEPA规定的可食用生物组织器官中BaP含量的上限值(0.67 ng·g-1,wetweight),对人体的致癌风险远小于10-5.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

土壤胡敏素对铜离子的吸附作用及其机理研究

以暗棕壤为供试土壤,研究了不同溶液pH值、离子强度、接触时间、反应温度和初始铜离子(Cu~(2+))浓度条件下,胡敏素对Cu~(2+)的吸附作用;利用扫描电子显微镜(SEM)、X-射线能量色散谱(EDS)、傅立叶变换红外光谱(FTIR)和X-射线光电子能谱(XPS),对胡敏素/胡敏素-Cu~(2+)复合物的表面形貌、元素分布和官能团组成进行了分析;应用延展X-射线吸收精细结构谱(EXAFS),对吸附态Cu~(2+)的局域配位结构进行了表征.结果表明:胡敏素对Cu~(2+)的吸附量随pH值、接触时间、反应温度和Cu~(2+)浓度的增加而增加,但随离子强度的增加而下降;吸附动力学符合准二级动力学方程,而吸附等温线用Langmuir方程的拟合效果较好;吸附过程需要能量,是自发、吸热和自由度增加的缔合反应;吸附Cu~(2+)之后,胡敏素表面产生了团聚现象,表面羧基、羟基、吡啶氮和N—O基团参与了Cu~(2+)的吸附作用,同时吸附态Cu~(2+)是以内层配位形式与胡敏素表面的O/N和C原子结合.     

Development and validation of LC-MS/MS method for the determination of Ochratoxin A and its metabolite Ochratoxin α in poultry tissues and eggs

The objective of this study was to develop a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the determination of Ochratoxin A (OTA) and Ochratoxin α (OTα) in poultry tissues and eggs. The two toxins were extracted by a mixture of acetonitrile/water, purified with a reversed phase C18 solid phase extraction column (SPE) and determined by LC-MS/MS. The LC-MS/MS method performances were evaluated in terms of linearity in solvent and in matrix (ranged from 0.5 to 15.10 µg L^?1 for OTA and from 0.60 to 17.85 µg L^?1 for OTα), limit of detection (LOD), limit of quantitation (LOQ), specificity, accuracy and precision in repeatability conditions. Recovery experiments were performed by spiking poultry liver, kidney, muscle and eggs around 1 µg kg^?1 and 10 µg kg^?1. LODs were 0.27 and 0.26 µg kg^?1 while LOQs were fixed at 1.0 and 1.2 µg kg^?1 for OTA and OTα, respectively. Main recoveries for OTA ranged from 82 to 109% and for OTα ranged from 55 to 89%. The values of within-laboratory relative standard deviation (RSD_r) were equal to or below 20%. Considering the results obtained and that all analytical performance criteria were fulfilled, the new extraction and purification method developed for OTA and OTα determination in animal tissues and eggs was found appropriate for control laboratories and research activities designed to ensure food safety.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

实验性糖尿病新西兰兔主要器官组织的病理学观察

将雄性新西兰兔随机分为:基础饲料组(即对照组:n=15)和高糖高脂饲料组(即实验组:n=15,喂食10％猪油,37％白蔗糖混合53％的基础饲料).共观察12周.于12周实验结束时,全部处死动物,取动物心脏、肝脏、胰腺、肾脏,用1O％福尔马林液固定,常规石蜡包埋切片,H、E染色,光学显微镜下观察并照相.结果表明:动物心肌细胞肥大,并出现灶性坏死,淋巴细胞浸润,心肌细胞间成纤维细胞增生和毛细血管增生,胶原纤维增加;肝细胞有明显脂肪变性,细胞肿胀;肾脏表现有肾小球球囊增大,细胞增多,毛细血管壁增厚,肾小管上皮细胞胞体增大;胰腺组织表现为胰岛分布稀疏,数量减少,胰岛萎缩,胰岛细胞数量减少,成纤维细胞增生.     

DIFFERENTIAL ACCUMULATION OF SELENIUM AMONG AXIAL MUSCLE,REPRODUCTIVE AND LIVER TISSUES OF FOUR WARMWATER FISH SPECIES1

Bluegill (Lepotmis macrochirus), largemouth bass (Micropterus salmoides), white catfish (Ictalurus catus), and channel catfish (Ictalurus punctatus), collected from an electric power plant cooling reservoir and a municipal water supply reservoir near Roxboro, North Carolina, were analyzed for selenium concentrations in axial muscle, reproductive and liver tissues. Fishes from the municipal water reservoir had lower selenium concentrations (≤0.2-2.1 μg/g - wet weight) than found in the cooling reservoir fishes (1.6-70.0 μg/g - wet weight) but similar distributions of concentrations among the tissues was evident. Selenium was differentially accumulated, with higher concentrations in liver tissues (0.7-70.0 μg/g - wet weight), followed by female reproductive tissues (0.7-25.0 μg/g - wet weight), axial muscle tissues (≤0.2-23.0 μg/g - wet weight) and male reproductive tissues (0.2-7.2 μg/g - wet weight).     

Trace elements in camel tissues from a semi-arid region

Trace and minor element concentrations differ in animal tissues as the result of the surrounding environment (feeding plants, soil contaminated with food and drinking water) and animal absorption of these elements. Concentrations of Ag, Au, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, and Zn were determined from different tissues of camel (inter-costal, scapula, sirloin, flank, front knuckle and front limb) from the semi-arid areas of the Aswan desert (Wadi El-Allaqi) and from Aswan city, Egypt. The study included an assessment of these same elements in the desert and city plants used as food by the camels and in soils from the study areas. The results reveal that camel tissues from the desert areas exhibited higher concentrations of Na, Mg, K, Au, Ag, Cu, Co and Zn than in those of the city camels. These higher levels of element are because of the high concentrations of the same elements in the desert plants and soil of the desert area. This, in turn, depends upon the geological formation differences between the desert area and the city area. Camel tissues appear to concentrate high levels of Mn, Ni, Co and Mg in the scapula while flank portions concentrate high levels of Mg and K. The levels of elements in the camel tissues under study were within the recommended safety baseline levels for camel health and human use, as well as within the appropriate limits in the desert and city plants for camel use.