Multimycotoxin UPLC-MS/MS for tea, herbal infusions and the derived drinkable products

In recent years the consumption of tea and herbal infusions has increased. These hot drinks are consumed as daily drinks as well as for medicinal purposes. All tea varieties (white, yellow, green, oolong, black and puerh) originate from the leaves of the tea plant, Camellia sinensis. All extracts made of plant or herbal materials which do not contain Camellia sinensis are referred as herbal infusions or tisanes. During processing and manufacturing fungal contamination of the plant materials is possible, enabling contamination of these products with mycotoxins. In this study a multimycotoxin UPLC-MS/MS method was developed and validated for the analysis of the raw tea and herbal infusion materials as well as for their drinkable products. The samples were analyzed by ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), with a mobile phase consisting of variable mixtures of water and methanol with 0.3% formic acid. The limits of detection for the different mycotoxins varied between 2.1 μg/kg and 121 μg/kg for raw materials and between 0.4 μg/L and 46 μg/L for drinkable products. Afterward 91 different tea and herbal infusion samples were analyzed. Only in one sample, Ceylon melange, 76 μg/kg fumonisin B(1) was detected. No mycotoxins were detected in the drinkable products.     

Variation in phenolic content and antioxidant activity of fermented rooibos herbal tea infusions: role of production season and quality grade

Data are required to calculate the dietary exposure to rooibos herbal tea flavonoids and phenolic acids. Representative content values for the principal phenolic compounds and total antioxidant capacity of fermented rooibos infusion, taking into account variation caused by production seasons (2009, 2010, and 2011) and quality grades (A, B, C, and D), were determined for samples (n = 114) from different geographical areas and producers. The major phenolic constituents were isoorientin and orientin (>10 mg/L), with quercetin-3-O-robinobioside, phenylpyruvic acid glucoside, and aspalathin present at >5 mg/L. Isovitexin, vitexin, and hyperoside were present at <3 mg/L. Rutin, ferulic acid, and isoquercitrin were present at <2 mg/L. Nothofagin was present at <1 mg/L. Only traces of luteolin-7-O-glucoside and the aglycones quercetin, luteolin, and chrysoeriol were present. Substantial variation was observed in the individual content values of the phenolic compounds and total antioxidant capacity within production seasons and quality grades.     

Nutritional and toxicological importance of macro, trace, and ultra-trace elements in algae food products

The content of 5 macro elements (Na, K, Ca, Mg, and P), 6 trace elements (Fe, Mn, Zn, Cu, Se, and I), and 4 ultra-trace elements (As, Pb, Cd, and Hg) in 34 edible dried seaweed products of brown algae (Laminaria sp., Undaria pinnatifida, and Hizikia fusiforme) and red algae (Porphyra sp.) originated from China, Japan, and Korea and bought by retail in Germany was determined. The content of these elements was analyzed by spectrometric methods (ICP-AES, ICP-MS, HGAAS, and CVAAS). Assuming a daily intake with 5 g FM of algae, the contribution of the essential elements to the diet is low, with the exception of I. Brown algae contained as much as 1316 +/- 1669 mg of I/kg FM. More than 4000 mg of I/kg FM were found in several Laminaria sp. Moreover, some brown algae, such as Hizikia fusiforme, had high contents of total As (87.7 +/- 8.2 mg/kg FM).     

微波消解—ICP-MS法测定有机肥料中8种元素

采用电感耦合等离子体质谱法(ICP-MS)测定,来比较不同混合酸体系对有机肥料中As、Pb、Cd、Cr、Hg、Ni、Cu、Zn 8种元素的提取效果,建立了微波消解—ICP-MS测定有机肥料多元素含量的方法。研究结果表明,8种元素在0.10～1600 μg/L质量范围内线性关系良好,线性相关系数为0.99970～0.99995,检出限范围为0.003～0.400 μg/L。三水平加标回收率范围为81.8%～108.0%,相对标准偏差为0.9%～4.9%(n=6)。国家标准物质灌木枝叶GBW07603(GSV-2)除汞元素缺少相应的认定值以外,其余7种元素的测定值均在标准物质证书认定值的范围内,且相对标准偏差为0.5%～5.0%(n=6)。该方法灵敏度、准确度高,可实现有机肥料中多元素的通量检测。     

Determination of trace elements in foods by HCl-HNO3 leaching and flame atomic absorption spectroscopy

Aluminum, iron, tin, zinc, calcium, magnesium, nickel, copper, chromium, cadmium, and potassium in foods can be extracted by HCl-HNO3 leaching and determined quantitatively using flame atomic absorption spectroscopy (AAS), with recoveries ranging from 90 to 110%. Thirty to 40 samples of almost any type of food sample can be analyzed routinely for 2 elements in 4-5 h. In contrast, one or 2 days are required when a wet-ash or dry-ash technique is used. Extraction consists of weighing 2-10 g samples into 125 mL Erlenmeyer flasks, adding 20 mL concentrated HCl-HNO3 (9 + 1), then heating in a 82- 93 degrees C water bath for 30 min. After cooling, samples are diluted to volume in 50 mL Nessler tubes and then filtered through No. 541 or 540 Whatman paper. The filtrate is analyzed directly by AAS.     

Patterns in trace elements in lichens

Water, Air, & Soil Pollution - Epiphytic lichens were sampled in a Dutch national monitoring survey, which was carried out twice within 5 yr. The samples were analyzed by neutron activation...     

Rare earth elements and other trace elements in wastewater treatment sludges

In order to evaluate the possibility of contamination of soil with trace elements by the application of sludges to soil, the contents of rare earth elements (REEs; La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) and other trace elements (Be, As, Ag, Cd, Sb, Cs, Bi, and U) in wastewater treatment sludges were determined. In sludges of night soil treatment plants (night soil sludges) and sludges of wastewater treatment plants in the food industry (food industry sludges), the distribution patterns of REEs normalized versus average REEs in the continental crust were almost flat. It was considered that the REE patterns of uncontaminated sludges reflected the pattern of the continental crust. The crust-normalized REE patterns of sludges of wastewater treatment plants in the chemical industry (chemical industry sludges) and municipal sewage sludges did not always show flat plots. The sludges that did not show a flat REE pattern were considered to be contaminated with some of the REEs.

The coefficient of variation of each element determined among the 10 samples of night soil sludges and the 14 samples of sewage sludges ranged from 34 to 77% and from 26 to 84%, respectively. Among the 10 samples of food industry sludges and the 10 samples of chemical industry sludges, the coefficient ranged from 60 to 143% and from 67 to 172%, respectively. The variations of the content of each element among the food industry sludges or the chemical industry sludges were larger than those among the night soil sludges or the sewage sludges.

The contents of Be, As, Cs, REEs, and U in all the sludges were lower than or the same as those in a field soil. Some of the food and chemical industry sludges contained larger amounts of Ag, Cd, and Sb than the soil. All the night soil sludges and sewage sludges contained much larger amounts of Ag and Bi than the soil.     

Characterization of major and trace elements in sclerotium grains

Sclerotium grains in soil contain humus-metal complexes that are probably produced from fungal metabolites. The characterization of major elements in sclerotium grains collected from volcanic ash soils in Mt Myoko was examined by X-ray photoelectron spectroscopy, FT-IR spectrometry and CHN analysis, and the concentration of trace elements was determined by PIXE (particle induced X-ray emission spectrometer) analysis. The content of major elements, C, H, N, O and Al, was approximately 47.6, 3.32, 0.78, 30.2 and 1.4% by mass, respectively. Trace elements such as Ti, Cr, Mn, Cu, Zn, Br and Pb were detected in the grains at concentrations between 10 and 100 μg g⁻¹. Functional carbon groups for the whole grain were characterized by the dominance of O-alkyl C associated with aromatic C. The comparison between the surface and subsurface (matrix) of the grain showed that the concentrations of O, C and N were relatively greater on the surface of sclerotium grains than in the matrix. The proportion of carbon having C–O, C=O, and O–C=O bonds, O and N showed a tendency to decrease from the surface towards the matrix. The proportion of C assigned as C–C and/or C–H bonds had a tendency to increase towards the matrix associated with Al.     

Determination of tea polyphenols and caffeine in tea flowers (Camellia sinensis) and their hydroxyl radical scavenging and nitric oxide suppressing effects

The native occurrence of tea polyphenols, namely, (-)-epicatechin, (+)-catechin, (-)-epigallocatechin 3-gallate, (-)-epicatechin, and (-)-epicatechin 3-gallate, and caffeine in tea flowers was assessed by an isocratic HPLC procedure. The levels of total catechins and caffeine were determined in tea flowers collected from 10 different species of Camellia sinensis. The results showed the levels of total catechin ranged from 10 to 38 mg/g, whereas the level of caffeine ranged from 3 to 8 mg/g. Levels of catechins and caffeine in tea leaves and various teas were also determined and ranged from 2 to 126 mg/g and from 23 to 49 mg/g, respectively. Both tea flower and tea leaf extracts exert their strong hydroxyl radical scavenging effects in the Fenton reaction system and nitric oxide suppressing effects in LPS-induced RAW 264.7 cells. Most tea flowers contain less caffeine, but comparable amounts of total catechins, compared to tea leaves and teas. The present study demonstrates that both tea flowers and tea leaves contain appreciable amounts of catechins and caffeine. It is likely that tea flowers might be useful for making alternative tea beverages.     

Factors affecting the caffeine and polyphenol contents of black and green tea infusions.

The effects of product and preparation variables on the in-cup chemical composition of tea extracts is of interest because the appearance and taste characteristics and the possible health effects of a tea liquor arise from the chemical components extracted from the leaf during tea preparation. A comprehensive study was therefore undertaken to determine the contributions of product and preparation variables on the total soluble solids, caffeine, and polyphenol contents of tea extracts. The results of this study show that the variety, growing environment, manufacturing conditions, and grade (particle size) of the tea leaves each influence the tea leaf and final infusion compositions. In addition, the composition of the tea infusion was shown to be influenced by whether the tea was contained in a teabag and, if so, the size and material of construction of the bag. Finally, the preparation method, including the amounts of tea and water used, infusion time, and amount of agitation, was shown to be a major determinant of the component concentrations of tea beverages as consumed. An illustration of the variation introduced by these product and preparation factors is provided by comparing solids, caffeine, and polyphenol contents of green and black tea infusions when commercial products are prepared according to the instructions given on their packaging.     

土垫旱耕人为土中某些痕量元素的迁移富集特征及其成因

土壤中元素的分布特征反映了多个成土因素综合作用下土壤发生过程的结果。为探讨人为因素和自然成土因素在土垫旱耕人为土(塿土)形成过程中的影响,本研究在黄土高原区关中平原西部的渭河三级阶地上采集两个典型的土垫旱耕人为土剖面,以马兰黄土作为成土强度的参照样品,采用Zr作为稳定元素,研究痕量元素Cu、Zn、Pb、Rb、Sr的分布特征及其成因。结果表明,受介质的吸附、碳酸钙等易淋溶组分的淋溶淀积、作物吸收等因素影响,痕量元素Cu、Zn、Pb、Rb在剖面上总体呈中高型分布,即在干润淋溶土表层(2A层)和黏质化B层(2B t层)含量有所增加而表现为富集;而Sr则发生强烈迁移,在2A层、2B t层含量显著降低。在埋藏耕作层(Aupb层)、亚耕层(Aup2层)和现代耕作层(Aup1层),自下而上,Cu、Zn、Pb的含量呈缓慢增加趋势,但只有Zn的富集系数在YL01剖面0~15 cm内大于1.1,说明土壤发生过程是导致土垫旱耕人为土剖面中某些层次元素相对富集的主要原因,而人类活动对土垫旱耕人为土痕量元素的影响很弱,且主要在表层。     

Source-receptor relationships for trace elements in Northern Europe

Measured air concentrations of several trace elements in southern Scandinavia have been related to long range transport and emissions of the same elements from sources in Europe using receptor modelling and statistical trajectory sector analysis. A good agreement, within a factor of 1.5 between estimates and measurements, has been obtained for Mn, Ni, Cu, and As. Significant differences were noted for V and Pb.     

Background levels of trace and ultra-trace elements in soils of Japan

Five hundred and fourteen soil samples collected from 78 sites in Japan were analyzed for their contents of trace and ultra-trace elements. We estimated the background levels (natural abundance) of 57 elements in soils. The concentration ranges were so wide that the ratios of the highest values to the lowest values were more than 100 for all the elements, with the exception of Be, Ga, Mo, Ag, In, Sn, and Ba. While the concentrations of the first transition elements (₂₁Sc to ₃₀Zn in atomic numbers) were higher than the concentration of the other elements, those of lighter (₃Li and ₄Be) and heavier elements tended to decrease, with an increase or decrease of atomic numbers, with the apparent exception of Pb, Th, and U. Concentrations of elements with even atomic numbers were, in most of the cases, higher than the concentrations of both adjacent elements with odd atomic numbers. Frequency distribution of most of the elements was strongly positively skewed. Markedly positive correlation coefficients (r>0.9) were observed among the elements within the same group in the Periodic Table in many combinations. The dendrogram obtained by cluster analysis showed that the occurrence and distribution of the elements in soils were mostly controlled by the chemical properties of each element, rather than by the nature and properties of individual soil samples. The total contents of the elements in soils were strongly dependent on the chemical composition of the parent rocks from which respective soils were derived.     

Principal component analysis of trace elements in Serbian wheat

Trace elements (Cu, Fe, Pb, Hg, Cd, As, Mn, Zn) were analyzed quantitatively in 14 wheat samples collected from fields in all Serbian growing regions, harvested in 2002. Microelements were determined according to an atomic absorption spectrophotometric method. Principal component analyses (PCA) were performed on data matrices consisting of contents of trace elements in wheats (columns) and all Serbian wheat-growing regions (rows). It was found that four principal components account for 87.2% of the total variance in the data. The plot of component loadings showed significant groupings for concentration of some microelements. The component scores indicated the similarities among the Serbian wheat-growing regions. The loading plot reveals that there is no need to measure all of the variables to achieve the same classification. It is enough to measure one variable per group. Naturally, this conclusion is valid only within the limits of the present study of wheat grain samples from different parts of Serbia.     

Effects of trace elements on urease activity in soils

Disposal of sewage sludges and effluents on agricultural land is becoming a widespread practice. Most sludge samples disposed on soils contain large quantities of various trace elements. Studies of 20 trace elements commonly found in sludge samples showed that they inhibit the activity of urease in soils and that their order of effectiveness as inhibitors of urease depends on the soil. When the trace elements were compared by using 5 μmiol·g^?1 soil, however, some of them showed the same order of effectiveness as urease inhibitors in the six soils studied i.e., for the monovalent and divalent ions, Ag⁺ ≥ Hg²⁺ >Cu²⁺ >Cd²⁺ >Zn²⁺ >Sn²⁺ >Mn²⁺, and generally, Fe²⁺ >Fe²⁺andCu²⁺ >Cu⁺. Other trace element ions that inhibited urease were Ni²⁺, Co²⁺, Pb²⁺, Ba²⁺, As³⁺ B³⁺, Cr³⁺, Al³⁺. V⁴⁺ Se⁴⁺ and Mo⁶⁺. Of the trace element ions studied, only As⁵⁺ and W⁶⁺ did not inhibit urease activity in soils.Studies on the distribution of urease activity showed that it is concentrated in surface soils and decreases with depth. Urease activity was proportional to organic C distribution in each soil profile and was significantly correlated with organic C in the surface soils studied.     

Determination of “normal” levels and upper limit values of trace elements in soils

To determine “normal” levels of trace elements in soils, soil samples taken all over Belgium were analysed. The selection of the sampling places was based on the geological substrata, from which the soils originate and on the texture class to which they belong. The elements As, B, Be, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Ti, V and Zn were determined using an extraction method with strong acids. The found concentrations were called “total acid extraction concentrations”, although this extraction does not extract all the elements which are incorporated into the minerals. This has been done, however, by arc emission spectrography which was applied to determine the elements Ag, B, Co, Cr, Ga, Mo, Ni, Sn, Sr and V. The greatest difference between the “overall total” concentrations and the “total extractable concentrations” were found for chromium. Based on the obtained results, an upper limit for normal levels of trace elements was fixed. For Ag, Cd, Hg, Pb and Sb, this upper limit value is almost the same for all the investigated soils irrelevant of their texture. The same conclusion could not be made for the other elements. For these elements, the soil texture and also the geological parent material, on which the soil was formed, have an influence on the upper limit value.     

Determination of Deposition and Leaves in Teak Plantations in Thailand

This paper outlines the results to date of the continuing acidic deposition study from 1997 in three teak plantations at the Na Pralan, Klangdong, and Donglan villages of Thailand. The aim of this study was to examine the impact on teak plantations of acid deposition — the increasing flow of chemical compounds including CO₂, SO₂, NO₂, and NO_x into the atmosphere. The 1997–1999 results showed no symptoms of acidity of the precipitation in the teak plantations at the treated sites (Na Pralan and Klangdong). During this period, the pHs of stemflow and throughfall were still over 7; and the pHs of the rainfall were around 7, except at Klandong where it dropped to around 5 in 1999. The pH and EC values were higher at the polluted sites than at the control site; this may be attributed to contamination with lime dust from nearby industrial plants, including cement factories and quarrying mills. Fresh leaves were contaminated with Sulphur to quite high levels at the Na Pralan site. This contamination seems to have affected the physiology, biomass and chemical content of the leaves. It might be due to pollution gases (SO₂ and NO_x) from the heavy trucks on the nearby Phaholyothin road. However, these gases could not be detected by a gas detector even though pollution seemed quite heavy. This study did not detect acid rain damage to the teak plantations.     

Mycotoxins in corn-based food products consumed in Brazil: an exposure assessment for fumonisins

Samples from 10 different corn-based food products commercially sold in the Federal District of Brazil were analyzed for fumonisins (FB1 and FB2) using HPLC/fluorescence following naphthalene-2,3 dicarboxaldehyde (NDA) derivatization (limit of quantification (LOQ) = 0.020 mg/kg). Samples were also analyzed for aflatoxins (B1, B2, G1, and G2) on a thin-layer chromatrography (TLC) plate under UV light (LOQ of 2 microg/kg). From the 208 samples analyzed, 80.7 and 71.6% had quantifiable levels of FB1 and FB2, respectively. Mean levels of total fumonisins (FB1 + FB2) ranged from 0.127 mg/kg for corn flakes to 2.04 mg/kg for cornmeal ( creme de milho). No FBs were detected in any of the fresh, sweet corn on the cob samples analyzed. Aflatoxins were not detected in any of the 101 samples analyzed. The daily intakes of fumonisins through the consumption of corn-based food products was estimated using consumption data estimated from the 2002/2003 Brazilian Household Budget Survey and the level of fumonisins found in this and other studies conducted in Brazil. In the Federal District, the calculated total daily intake for the total and the consumers-only populations represented, respectively, 9.0 and 159% of the provisional maximum total daily intake (PMTDI) of 2 microg/kg body weight per day. At the national level, the intakes were calculated based on the fumonisin levels found in the Federal District and on published data from studies conducted elsewhere in the country. They represented 24.1 and 355% PMTDI for the total and the consumers-only populations, respectively. The high incidence of fumonisins in some corn-based products and the exposure levels found for specific subpopulations in the present study indicate the need for setting safe regulatory levels for fumonisins in food in Brazil.     

Immunomodulatory effects of cadmium and Gynostemma pentaphyllum herbal tea on rat splenocyte proliferation

Gynostemma pentaphyllum Makino (GP) is a herbal tea widely grown in Southeast Asia. However, this herbal tea can be contaminated with some heavy metals, especially cadmium (Cd), from agricultural areas, which may affect human health. The objective of this study is to evaluate the immunomodulatory effects of Cd contaminated in GP herbal tea and inorganic Cd on rat splenocytes. Rats were divided into groups and treated with drinking water (control), high CdCl 2 in drinking water (HCd; 0.05 mg/L), GP herbal tea containing 0.05 mg/L Cd (GP-HCd) for 4 months, low CdCl 2 in drinking water (LCd; 0.006 mg/L), and GP herbal tea containing 0.006 mg/L Cd (GP-LCd) for 6 months. After the treatments, Cd accumulation in organs and blood was detected by using a graphite furnace atomic absorption spectrophotometer. In spleen, HCd-treated rats had 4-fold higher Cd accumulations than GP-HCd-treated rats. Cd accumulation in liver and kidney in the HCd group also increased significantly. There were no significant changes in total leucocyte and lymphocyte counts; however, these parameters tended to decrease slightly in LCd, GP-LCd, and GP-HCd groups. The HCd group (ex vivo) significantly produced suppressive effects on T cell mitogen-induced splenocyte proliferation, with 1 mug/mL Con A and PHA-P. In addition, 0.5 mug/mL PWM-induced B cell proliferation, through T cell functions, was also significantly inhibited by HCd as compared to the control group, while GP-HCd had no effects. However, both GP-LCd- and LCd-treated rats had a slight increase in Con A-stimulated splenocyte proliferation. This study indicated that high Cd contamination in drinking water alone had suppressive effects on T cell functions, but these effects could not be found with the same Cd level contamination in GP herbal tea.