Analysis of element species fractions in buckwheat and amaranth flours by SEC/ICP-MS and MALDI-MS

Fractionation of Co, Cu, Fe, Mn, Mo, Ni, P and Zn in extracts of buckwheat and amaranth flour in 0.02 mol·l⁻¹ Tris-HCl (pH = 7.5) buffer was performed by SEC/ICP-MS. All metals except for Fe and Mn (both samples) and Cu (amaranth only) are concentrated in a low-molecular fraction (M _r < 2 kDa). Fe is bound in a high-molecular fraction (M _r > 150 kDa). The main part of Mn is present as a labile complex or an ionic form. Cu in amaranth extract is also bound in medium-molecular fractions (10 and 40 kDa) and in a high-molecular one (M _r > 150 kDa). Fractions rich in trace metals were isolated using preparative-scale SEC and the organic ligands of metals were refined by immobilized metal affinity chromatography. Low content of sulphur-containing amino acids (Cys, Met) and high content of acidic amino acids (Glu, Asp) are typical for all these purified fractions. A part of Zn (buckwheat) and almost all Cu (amaranth) in the low-molecular fractions were located in phosphorus rich sub-fractions. However, all Ni (both samples), the majority of Zn (buckwheat) and all Cu (buckwheat) were found in phosphorus-less sub-fractions. No phytochelatins were found in MALDI-MS spectra of isolated ligands.     

Heavy metals in some edible mushrooms from the Central Anatolia,Turkey

Eight trace elements (Pb, Cd, Zn, Fe, Mn, Cu, Cr and Ni) in 15 different wild-growing edible mushroom species collected from Eski?ehir, Turkey were determined. The highest Pb, Fe, Mn and Cu concentrations were 11.72, 11460, 480 and 144.2 mg/kg (dry weight basis), respectively. All of these highest metal concentrations were determined in Lepista nuda. Cadmium and chromium were determined at the highest concentrations in Gymnopus dryophilus, 3.24 and 73.8 mg/kg, respectively. The highest zinc and nickel content were observed in Tricholoma equestre and Coprinus comatus as 173.8 and 58.60 mg/kg dry matter, respectively. Mushrooms species determined as important metal accumulators were L. nuda, G. dryophilus, T. equestre and C. comatus, in this study. Heavy metal contents of all analysed mushrooms were generally higher than previously reported in the literature.     

Metal levels in economically important bivalve species from Turkey

Concentrations of eight heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) were determined in economically important bivalve species: oyster (Ostrea edulis), wedge clam (Donax trunculus), manila clam (Ruditapes philippinarium) and warty clam (Venus verrucosa) from the Marmara and Aegean seas. Samples were collected seasonally between 2008 and 2009. Metal levels of bivalves were found in the following ranges: As 0.02–3.40, Cd 0.02–2.80, Cr 0.19–0.82, Cu 0.82–25.06, Hg?<?LOD–0.12, Ni 0.09–0.73, Pb 0.05–4.16 and Zn 6.85–899?mg?kg^?1. The most abundant elements were Zn?>?Cu?>?As. In addition, the results showed that oysters had the highest concentrations of Zn in all seasons. The next abundant heavy metal detected was Cu in oyster and other clam species. It was concluded that in the future, these metals should be monitored regularly.     

Heavy metals concentrations in dairy cow feedstuffs from the south of Iran

ABSTRACT

Levels of lead, cadmium, mercury, copper and zinc elements in feedstuffs were measured by inductively coupled plasma-optical emission spectrometry. A total of 216 feedstuffs samples including corn silage, alfalfa hay, wheat straw, full ration pellet, wheat bran and barley were collected from polluted and unpolluted regions during four seasons and prepared with wet digestion. Lead and mercury concentrations did not differ significantly in various feedstuffs, but cadmium level was significantly the highest in barley samples (p < 0.05). All feed material samples had lead, cadmium and mercury concentrations well below the maximum levels allowed by the European Union. The lowest and highest levels of both copper and zinc were found in wheat straw and wheat bran, respectively, but their maximum content did not exceed the legal limits. In contrast to the sampling area, season significantly (P < 0.05) affected heavy metal levels, except for zinc, in feedstuffs.     

Copper in foods,beverages and waters from South East Spain: influencing factors and daily dietary intake by the Andalusian population

The copper content of 225 food, 49 beverage and twelve potable water samples were determined using atomic absorption spectrometry (AAS). Analyses of NIST and BCR reference materials demonstrated the accuracy of this technique. The highest copper levels were found in dried fruit and legumes, followed by organ meats, molluscs and crustaceans, cephalopods, cereals and sausages, respectively. In cereals, legumes and fruit, copper levels increased significantly with increasing levels of protein and decreasing carbohydrate content (p?<?0.001). In meat and meat by-products, copper concentrations found in organ meats were significantly higher (p?<?0.01). In fresh fish products, copper levels in shellfish were significantly higher than those measured in fish (p?<?0.001). In vegetables, the copper concentrations found in mushrooms were significantly higher (p?<?0.005). Mean copper concentrations analysed in cheese were statistically higher than those determined in other dairy products (p?<?0.01). In beverages, copper levels determined in rum and juices were significantly higher (p?<?0.001). Beverages for which a vegetable component was directly used in their manufacturing process (juices, wines and beers) had statistically higher copper levels when compared with fresh drinks. The daily dietary intake (DDI) of copper in the Andalusian diet was 1979 μg day^?1 per person. Cereals, meat, meat by-products and vegetables are the food categories that are the main source of copper in the daily diet. Taking into account the dietary reference intakes and upper levels (900 and 10, 000 μg Cu day^?1 for healthy adults, respectively), the mean copper DDI found indicate that for most of healthy adult individuals from the area, no adverse effects occur in relation to copper nutrition (deficiency or toxicity). Potable waters supplied 53 μg day^?1, which constitutes on average 0.025% of the maximum tolerable daily intake of this element set by the Joint FAO/WHO Expert Committee.     

The effects of sex and seasonality on the metal levels of different muscle tissues of mature Atlantic blue crabs (Callinectes sapidus) in Mersin Bay,north‐eastern mediterranean

The objective of this study was to determine the seasonal and sexual effects on metal levels of lump crabmeat (LCM) and chela crabmeat (CCM) of mature Atlantic blue crabs, Callinectes sapidus, caught in the Mersin Bay, the north‐eastern Mediterranean. The findings indicated that the annual ranges of metal levels in the LCM of Atlantic blue crab were as follows: 0.44–0.61 μg Cd g^?1, 0.30–0.60 μg Cr g^?1, 0.24–0.52 μg Pb g^?1, 9.72–43.70 μg Cu g^?1, 39.52–97.26 μg Zn g^?1, 11.97–32.48 μg Fe g^?1. The annual range of metal levels in the CCM of Atlantic blue crab were as follows: 0.52–1.07 μg Cd g^?1, 0.24–0.61 μg Cr g^?1, 0.28–0.56 μg Pb g^?1, 22.17–68.09 μg Cu g^?1, 93.92–175.21 μg Zn g^?1, 8.81–19.47 μg Fe g^?1. Cd, Cu, Zn levels in CCM of Atlantic blue crabs were higher than in LCM, whereas Fe levels were found lower (P < 0.05). Fe metal specifically accumulated in LCM, and Cd, Cu and Zn metals accumulated in CCM. Metals such as Cu, Zn and Fe showed seasonal variations. It was found out that Cu, Zn and Fe levels of muscle tissues of the Atlantic blue crab in spring and summer seasons were higher than in autumn and winter seasons.     

Genetic and environmental variability in starch,fatty acids and mineral nutrients composition in cowpea (Vigna unguiculata (L) Walp)

Fifteen cowpea cultivars grown in three locations (Kano (12°00′N 8°31′E), Mokwa (9°17′N 5°04′E) and Ago-Iwoye (6°58′N 4°00′)) between 1993 and 1994 were analysed for genotype, environmental and genotype×environment variability for starch (g kg⁻¹), fatty acids (% of total oil) and mineral nutrients (g kg⁻¹) composition. There were significant environmental as well as genetic effects on these nutritional qualities. The environmental effect accounted largely for the variability observed in starch (60%), palmitic acid (80%), arachidic acid (100%), potassium (100%), phosphorus (81%) and manganese (86%), while the genotypic effect accounted largely for the variability observed in linoleic acid (50%), linolenic acid (50%) and copper (68%) contents. Correlation coefficient (pooled data) from the three locations indicated that starch was positively correlated to palmitic acid (r = 0·21, 0·01< P < 0·05), potassium (r = 0·80, P < 0·001) and phosphorus (r = 0·65, P < 0·001), but negatively correlated to oleic (r = −0·23, 0·01< P < 0·05), linoleic (r = −0·67, P < 0·001) and linolenic acid (r = −0·74, P < 0·001) contents. Starch showed a strong positive correlation with magnesium content (r = 0·75) and a strong negative correlation with copper (r = −0·73) and iron (r = −0·62) at the genetic level. This research established the degree of variability for these characters in cowpea. © 1998 Society of Chemical Industry.     

Analysis of total and dialyzable copper levels in duplicate meals by ETAAS: daily intake

The determination of total and dialyzable copper levels of 108 hospital meals by the duplicate diet sampling method was performed. The analysis of Cu levels was done by an electro thermal atomic absorption spectrometry (ETAAS) method developed. The criteria for the validation of the method [sample recoveries, repeatability, limit of detection, sensibility and analyses of the standard reference materials (BCR CRM 063R and CRM 185R)] demonstrated its reliability and accuracy. The total Cu supply by meals is directly and significantly (P < 0.001) correlated with their macronutrient contents. The mean total and dialyzable Cu levels were 314.0 ± 123.2 μg and 84.19 ± 50.96 μg, respectively. The mean dialysis Cu percentage was 25.95 ± 15.70%. The total and dialyzable Cu levels and dialysis Cu percentages (Cu bioaccesability) found in breakfasts were significantly lower (P < 0.001). The dialysis Cu levels enhance significantly with the total element contents. The dialysis Cu levels and dialysis Cu percentages present in meals were primary and significantly correlated with carbohydrates, fibre, P, Fe, cholesterol, protein and several amino acids (P < 0.01). Food like cereals, legumes and dry fruits are primary sources of bioaccesible Cu in the diet. The protein and derivate amino acids, previous digestion, form soluble complexes with Cu in the gastrointestinal tract enhancing significantly the element bioavailability. Dialyzable Cu levels and dialysis Cu percentages enhanced significantly with corresponding Cr levels of meals (P = 0.001). The mean Cu daily dietary intake (DDI) found was 941.5 μg/day. The method of duplicate diet sampling and analysis of Cu facilitates the most accurate and reliable results and considers the influence of technological and cooking processes. The Cu DDIs reported indicate that probably no problems in relation to Cu nutrition could be observed in usual consumers of these meals (users and staff of the hospital).     

Studies on protein and its high‐molecular‐weight subunit composition in relation to chapati‐making quality of Indian wheat cultivars

In order to predict the suitability of wheat for chapati making, 15 Indian wheat cultivars were studied for various protein characteristics in relation to chapati‐making quality. The cultivars varied considerably in their protein characteristics and chapati‐making potential. Results clearly indicated that both quantitative and qualitative characteristics of proteins influenced the chapati‐making potential of cultivars. Puffed height, the important qualitative parameter of chapati, was positively correlated with protein content (r = 0.62, p < 0.05), gluten content (r = 0.79, p < 0.01), sodium dodecyl sulphate (SDS) sedimentation value (r = 0.57, p < 0.05) and Glu‐1 quality scores of high‐molecular‐weight (HMW) subunits (r = 0.66, p < 0.01). Overall quality score of chapati was positively correlated with gluten content (r = 0.64, p < 0.01), SDS sedimentation value (r = 0.60, p < 0.05) and Glu‐1 score (r = 0.58, p < 0.05). HMW subunit composition varied considerably among cultivars. Cultivars having 5 + 10 subunits at the Glu‐1D chromosome, a protein content of about 130 g kg^?1 and SDS sedimentation value around 75 ml yielded excellent chapatis, while those having 2 + 12 subunits, a protein content of about 115 g kg^?1 and SDS sedimentation value around 55 ml resulted in poor chapatis. Interestingly, the presence of the 1BL/1RS chromosome in cultivars had no adverse effect on chapati quality. © 2003 Society of Chemical Industry     

Mineral contents of 34 species of edible mushrooms growing wild in Turkey

Mineral contents of 34 species of wild mushrooms, growing particularly in the central Anatolia region in Turkey, were determined by inductively coupled plasma atomic emission spectrometry (ICP‐AES). All mushrooms contained high amounts of Al, Ca, Fe, K, Mg and P. The highest potassium level was 45189.4 mg kg^?1 for the species Coprinus micaceus, whereas the lowest K content was 9973.8 mg kg^?1 in Polyporus squamosus. Among the wild mushrooms, the highest lead level was 5.4 mg kg^?1 in the species Helvella leucomelano. Iron contents of mushrooms were found in similarly small percentages in all the species analysed, ranging from 338.3 mg kg^?1 in Russula delica to 8994.71 mg kg^?1 in Helvella spadicea. Phosphorus content ranged from 2095.6 mg kg^?1 in Polyporus squamosus to 22799.0 mg kg^?1 in Helvella spadicea. Magnesium was found to be high, ranging from 458.1 mg kg^?1 in Rhizopogon luteolus to 4254.9 mg kg^?1 in Morchella esculenta. This study attempts to contribute to knowledge of the human nutritional properties of these mushroom species, and may be useful for the evaluation of dietary information. Copyright © 2006 Society of Chemical Industry     

Trace metal levels in mushroom samples from Ordu,Turkey

The concentrations of Fe, Mn, Zn, Cu, Pb, Cd, Cr, Ni in mushroom species of Turkish origin were determined by atomic absorption spectrometry after microwave digestion. The mushrooms were collected from Ordu, Turkey. The highest Fe level was 628 mg/kg in Mycena inclinata. The highest Mn levels was 103 mg/kg in Coprinus comatus. Zn level was 162 mg/kg in Panellus stipticus. Cu level was 86.2 mg/kg in M. inclinata. Pb level was 11.4 mg/kg in P. stipticus. Cd level was 1.6 mg/kg in Panaeolus campanulatus. Cr level was 4.4 mg/kg in C. comatus and Ni level was 21.6 mg/kg in M. inclinata.     

Phenolics and in-vitro degradability of protein and fibre in West African Browse

Relationships among soluble phenolics, soluble and insoluble proanthocyanidins (PAC), lignin, N, neutral-detergent fibre (NDF), and in-vitro degradability of protein and NDF were determined in 72 West African fodder trees and shrubs. Species were collected in the semi-arid (Niger), sub-humid (Nigeria) and humid/sub-humid (Benin) zones. Variation among species in chemical composition and in-vitro degradability of protein and NDF was large. Zones did not differ in mean content of phenolic compounds. Protein degradability was negatively correlated with soluble phenolics (r = ?0.34, P < 0.01) and soluble PAC (r = ?0.47, P < 0.001). NDF was positively correlated with soluble PAC (r = 0.44, P < 0.001), insoluble PAC (r = 0.28, P < 0.05) and lignin (r = 0.76, P < 0.001). NDF degradability was negatively correlated with soluble PAC (r = ?0.40, P < 0.001) and lignin (r = ?0.59, P < 0.001). Chemical composition and in-vitro degradability along with field observations can provide useful criteria for determining the nutritive value of browse species.     

Antioxidant responses of some common medicinal plants grown in copper mining areas

The effect of bioaccumulated Cu on the antioxidant properties of medicinal plants grown in Cu rich soil is studied. The total phenolic and flavonoid content, 2,2′-Diphenyl-1-picrylhydrazyl (DPPH•) scavenging activity, reducing power, metal chelating activity and inhibition of lipid peroxidation were assayed in methanol (MeOH) extracts of eight medicinal plants grown in the vicinity of copper mining impact site and compared with control samples. Corresponding IC₅₀ values of DPPH• scavenging ability and metal chelating ability were found to be significantly (P < 0.05) higher in mining impact samples e.g., Withania somnifera, Azadirachta indica, Andrographics peniculata and Ocimum sanctum. The IC₅₀ of inhibition of lipid peroxidation of all the mining impact samples were significantly (P < 0.05) higher than the control samples, indicating lower inhibition capacity of lipid peroxidation by the mining impact samples. This was attributed to higher Cu contents in the MeOH extracts of mining impact samples measured by inductively coupled plasma mass spectrometry (ICP-MS).     

A survey of selected heavy metal concentrations in Wisconsin dairy feeds

Heavy metals such as zinc (Zn), copper (Cu), chromium (Cr), arsenic (As), cadmium (Cd), and lead (Pb) are potential bioaccumulative toxins of the dairy production system. The heavy metal content of dairy feeds, however, remains poorly documented, particularly in the United States. This survey determined the heavy metal content of 203 typical dairy ration components sampled from 54 dairy farms in Wisconsin. Lowest heavy metal concentrations were found in homegrown alfalfa (Medicago sativa L.) hay and haylage, and corn (Zea mays L.) grain and silage. Highest metal concentrations were found in purchased feeds, particularly mineral supplements, and to a lesser extent corn- or soybean-based concentrates. Zinc and Cu were found at the highest concentration in complete dairy (total mixed and aggregated component) rations and reflected the deliberate addition of these metals to meet animal nutrient requirements although more than half the farms fed Cu and Zn above US recommended levels. Concentrations of Cr, As, Cd, and Pb were present in much lower concentrations and decreased in the order Cr > As > Pb > Cd. No complete Wisconsin dairy ration contained heavy metal concentrations above US maximum acceptable concentrations and would be unlikely to induce any toxic effects in dairy cattle. Concentrations of Cd in complete dairy rations were closest to US maximum acceptable concentrations, suggesting the greatest potential long-term risk to exceed US maximum acceptable concentrations if whole farm levels of Cd were to increase in the future. With the exception of Pb, the main sources of Zn, Cu, Cr, As, and Cd in the complete dairy feed ration originated from imported feed. The continued importation of heavy metals in dairy feed is likely to be associated with accumulation of these metals in soils where manure is applied. Although the cycling of many heavy metals through the dairy food chain will be limited by factors such as a soil's cation exchange capacity, pH, salinity, and phytotoxicity of the metal, these may be less limiting for Cd. It is important that sources of Cd in the dairy system are identified and minimized to prevent problems associated with Cd accumulation in the dairy soil system arising over the long-term.     

Impact of Precursors Creatine,Creatinine, and Glucose on the Formation of Heterocyclic Aromatic Amines in Grilled Patties of Various Animal Species

The impact of precursors such as creatine, creatinine, and glucose on the formation of mutagenic/carcinogenic heterocyclic amines (HAs) were studied in patties of 9 different animal species equally heat treated with a double‐plate contact grill. All grilled patties of the various species (veal, beef, pork, lamb, horse, venison, turkey, chicken, ostrich) contained several HAs such as MeIQx (2‐amino‐3,8‐dimethylimidazo[4,5‐f] quinoxaline; 0.5‐1.4 ng/g), 4,8‐DiMeIQx (2‐amino‐3,4,8‐trimethylimidazo[4,5‐f] quinoxaline, 0 to 1.3 ng/g), PhIP (2‐amino‐1‐methyl‐6‐phenylimidazo[4,5‐b] pyridine, 1.2 to 10.5 ng/g), harman (1‐methyl‐9H‐pyrido[3,4‐b] indole; 0.5 to 3.2 ng/g), and/or norharman (9H‐pyrido[3,4‐b]indole 0.5 to 1.9 ng/g). Residual glycogen (glucose) content varied greatly from 0.07 to 1.46 wt% on a dry matter (DM) basis. Total creatin(in)e content in raw meat (1.36 to 2.0 wt% DM) hardly differed between species, except in turkey and ostrich (1.1 wt% DM). Chicken contained, compared to all other species, very low concentrations of glucose (0.07 wt% DM) and the highest levels of nonprotein nitrogen compounds. The free amino acids lysine (r = 0.77, P < 0.001), tyrosine, phenylalanine, proline, isoleucine, and aspartic acid (r = 0.47–0.56, P < 0.05) showed significant correlation to PhIP in chicken. Also a linear correlation was found to exist between PhIP (r = 0.87, P < 0.001) and MeIQx (r = 0.35, P < 0.01), and the molar ratio of creatin(in)e to glucose, respectively. Harman as co‐mutagens was linearly correlated to the concentration of glucose (r = 0.65, P < 0.001). By contrast, norharman was not significant correlated to glucose levels.     

Effect of high oxygen modified atmosphere on post‐harvest physiology and sensorial qualities of mushroom

The changes in physiology and sensorial qualities of mushroom stored at 2 °C for 12 days under high oxygen (100% O₂, 80% O₂) atmosphere and air had been investigated. Respiration rate was suppressed in mushroom in 80% O₂ and 100% O₂. No significant differences were found between 80% O₂ and 100% O₂. Weight loss was not more than 1.5% in all treatments. Weight loss and firmness of mushroom held in high oxygen were significantly (P < 0.05) higher than in air. Total soluble solid (TSS) was only slightly affected by high oxygen treatment. High oxygen, especially 100% O₂ treatment was effective at reducing browning degree and electrolyte leakage of mushroom. The surface colour of mushroom changed slightly before tenth day under high oxygen treatment. From day 2 the L‐value of mushroom flesh was significantly (P < 0.05) lower under air atmosphere compared with high oxygen treated mushroom. High oxygen, especially 100% O₂ was effective at inhibiting discoloration. The PPO activity of mushroom was significantly (P < 0.05) higher in 100% O₂ compared with air treatment. The POD activity was highest in high oxygen at eighth day, then reduced. High oxygen, especially 100% O₂ was effective at maintaining the quality of mushroom.     

Heavy Metal in Edible Portions (Muscle and Skin) and Other Organs (Gill,Liver and Intestine) of Selected Freshwater Fish Species

In this study, the concentrations of copper, zinc, manganese, iron, cobalt, calcium, magnesium, nickel, lead, chrome and boron elements in muscle, gill, skin, intestine and liver of selected fish species (Rutilus rutilus, Carassius carassius, and Cyprinus carpio) from Porsuk Dam Lake/Turkey were determined. The element analyses were performed with inductive coupled plasma-optic emission spectroscopy following microwave digestion techniques. Metal accumulation levels of tissues and species were remarkably different. Concentrations of Ni, Pb, Cr and B in all tissues of the species were found to be below the detection limit (BDL) with ICP-OES. Irrespective of the fish species and tissues, the concentrations (mg kg^?1 wet weight) of the other matals varied in the following ranges: Cu, below detection limit (BDL)-17.15; Zn, 9.08–699.60; Mn, BDL-8.23; Fe, 4.42–137.17; Co, BDL-1.49; Ca, 144.40–14376.60 and Mg, 95.81–903.23. The metal levels in muscle of the species were found below the limits proposed by FAO, WHO, and Turkish Food Codes, and these are safe for human consumption. However, heavy metal accumulation in skin and liver of some species was as high as non-permitted limits.     

Potentiometric stripping analysis of selected heavy metals in biological materials

Different biological materials such as edible oils, refined and unrefined cane and beet sugar and tea (black and green) leaves were assayed for the heavy metals cadmium, copper, lead and zinc. The results revealed significant differences in heavy metal contents within each class of the biological materials (P < 0.05). Cadmium was not detectable in sugar samples. Among the oils, highest amounts of copper (0.263 μg/g) and lead (0.154 μg/g) were in corn oil and zinc in olive oil (3.01 μg/g) whereas cadmium exhibited a narrow range (0.023–0.033 μg/g). The samples of beet-sugar generally contained higher levels of the heavy metals than cane-sugar. Black and green tea leaves contained 0.411–0.908 μg Cd/g, 6.500–9.220 μg Cu/g, 2.200–5.238 μg Pb/g, and 14.500–25.180 μg Zn/g.     

Metal Contents,Bioaccumulation, and Health Risk Assessment in Wild Edible Boletaceae Mushrooms

Eight wild edible Boletaceae mushrooms (227 samples) and their soils were collected from 40 locations, Yunnan province, China. Four essential metals (Fe, Mg, Zn, and Cu) and 2 toxic metals (Pb and Cd) were determined. The results showed that Boletaceae mushrooms have abundance of 4 essential metals. The highest Pb mean value was 0.70 mg/kg DW, lower than legal limits, but Cd contents significantly exceeded legal limits. Generally, bioconcentration factor (BCF) indicated that Zn and Cu were easily bioaccumulated by mushrooms. However, the BCF_Cd of Boletus griseus reached to 6.40. Target hazard quotients showed Cd was the main risk metal in Boletaceae mushrooms. The metal compositional variability and the similarity of metal contents were further determined by principal component analysis. Regression model analysis indicated that Cd contents in mushrooms were positively correlated with soil Cd contents, and negatively correlated with soil pH, except for the samples of Boletus bicolor.