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Feasibility study prior to the certification of trace elements in urban and industrial wastewater reference materials.

Reliable results for the determination of trace elements in urban and industrial wastewaters are of paramount importance for both checking the performance of sewage treatment and for detecting possible urban or industrial contamination sources. The quality control of measurements should in principle rely on external tools such as certified reference materials (CRM), which should represent, as closely as possible, the matrix of samples currently analysed, e.g., in the frame of environmental monitoring. To date, however, no CRM representatives of wastewater composition are available, which limits the possibility for control laboratories to check their QC externally. To fill this gap, the European Commission's Standards, Measurements and Testing Programme (formerly BCR) has started a European collaborative project of which the aim is to test the feasibility of preparation of wastewater reference materials and the analytical state-of-the-art to enable the certification of trace elements in such matrices. This paper presents the results of the first phase of this project, namely the feasibility study and the results of an interlaboratory trial.

Certification↗

[Intake of trace elements and heavy metals with the diet of 2-14 years old children. Zinc, manganese, copper, fluoride, iodine, selen; lead, cadmium, mercury (author's transl)].

For 2-14 year old children the intake of the trace elements zinc, manganese, copper, fluoride, iodine, selen, and of the heavy metals, lead, cadmium and mercury is calculated from their food intake. The results give a representative statement of the average supply of trace elements and of the average intake of heavy metals with the diet of children in the Federal Republic of Germany. It is shown that the choice of foodstuffs for the diet has an important influence on the supply of trace elements.

Adolescent↗

Selected vitamins and trace elements in blood of vegetarians.

Selected vitamin (A, C, E, beta-carotene) and trace element (selenium, zinc, copper) levels were estimated in the blood of 67 vegetarian nonsmokers aged 34-60 years. The average period of lacto- or lacto-ovovegetarianism was 6.2 years. The results were compared with those of 75 nonvegetarians of the same age and living in the same region. Vegetarians had significantly higher plasma levels of essential antioxidants: vitamin C, beta-carotene, and vitamin A. A significantly higher molar ratio vitamin E/cholesterol indicates a more effective protection especially of low-density lipoproteins against peroxidation. Oxidation of low-density lipoproteins represents one of the key factors in the pathogenesis of atherosclerosis. The molar ratio vitamin E/total lipids was significantly higher in plasma of vegetarians, demonstrating a more effective protection of polyunsaturated fatty acids against peroxidation. Vegetarians had significantly higher plasma levels of selenium and similar levels of zinc and copper when compared to nonvegetarians. These trace elements are important for the activity of antioxidant enzymes. The results document a beneficial effect of vegetarian nutritional habits on antioxidative parameters and thus on the reduction of cardiovascular diseases and cancer risk. Reactive products of oxygen metabolism and subsequent toxic products of lipid peroxidation play an important role in the etiology of these diseases.

Adult↗

The role of trace elements in juvenile diabetes mellitus.

There is accumulating evidence that the metabolism of several trace elements is altered in insulin-dependent diabetes mellitus and that these nutrients might have specific roles in the pathogenesis and progress of this disease. Magnesium deficiency is the most evident disturbance of metal metabolism in diabetes mellitus. Hypomagnesemia might increase the risk of ischemic heart disease and severe retinopathy. Increased urinary loss of zinc is a commonly encountered feature of diabetes. High-dose oral zinc might enhance wound healing, although data regarding diabetes are lacking. Chromium increases tissue sensitivity to insulin and tends to raise high-density lipoprotein (HDL) cholesterol and the HDL:low-density lipoprotein ratio. Selenium is involved in processes which protect the cell against oxidative damage by peroxides produced from lipid metabolism. There is one report of elevated serum selenium in diabetic children although the clinical significance of this finding is still unclear. An insulin-like effect has recently been attributed to vanadium in experimental animals, a finding of potential interest to man. Current knowledge does not implicate iron, iodine, manganese, cobalt, nickel, silicone, fluoride, molybdenum or tin in the pathophysiology of diabetes. Appropriate trace element supplementation might prove beneficial in ameliorating some physiological deficiencies associated with diabetes and prevent or retard secondary complications. However, properly designed and well-documented trials, especially on magnesium supplementation, need to be performed before rationales for such supplementation are developed. The potential roles of vanadium, chromium and selenium in diabetes constitute challenging areas for further experimental and clinical research.

Animals↗

Direct determination of selenium and other trace elements in serum samples by ICP-MS.

Selenium belongs to a group of trace elements of special interest in biological samples for clinical diagnosis. Selenium has antioxidizing functions and is essential for providing the organism with triiodothyronine produced from thyroxine. Among several analytical techniques used to determine the Se concentration in serum, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) has been used in the past because of its high sensitivity. Interference problems originating from different ions on the major Se isotopes have been described to be a limiting factor for the direct determination of Se in these matrices. Standard addition calibration or isotope dilution is often required to overcome carbon-enhanced ionisation effects in biological sample matrices. In most cases, the typical serum sample volume which is available for the analysis is limited to 0.5 ml or less, making multiple sample preparation for standard addition calibration impractical. Isotope dilution requires enriched isotopes and substantial sample preparation. Furthermore, the approximate Se concentration in every sample has to be known to adjust the appropriate amount of spike to each sample. Matrix matching with methanol has been described to overcome ionisation effects but we found limiting factors of this application when other trace elements are also determined within one sample run. This paper describes an effective sample preparation method which allows the direct determination of Se in serum without limiting the analytical capabilities for the additional determination of Al, Cu, Ni, Co, Cd, Mn and Zn in a single sample run by ICP-MS. Optimization procedures are presented and results of the analysis of reference samples are discussed, with a comparison of more than 150 serum data with those obtained by the GF-AAS method.

Animals↗

The effect of peat components on endocrine and immunological parameters and on trace elements--results of two pilot studies.

Peat and different peat preparations are successfully used in clinical therapies for different indications (as, for instance, in the field of gynecology). New studies show the biochemical effects of peat components which they have aside from their physical-thermal effects. This is of extraordinary interest with regard to the medical use of peat, because considerable concentrations of trace elements and heavy metals have been found in different kinds of peat. By means of atomic spectrometry it was investigated in 17 female patients with irritable bladder whether and how variations of the concentration of special trace elements and heavy metals (lead, cadmium, copper, manganese) could be measured within 24-hour urine after vaginal peat-mush treatments had been applied serially. Additionally, the effect of peat-mush baths compared to the effect of water baths (n=6) - both of which were applied to 17 female patients with degenerative diseases - was examined with regard to their special endocrinological parameters. The results concerning safety did not show any changes of the concentration of the trace-elements or heavy metals within the 24-hour urine. These results can be explained by the chelating features of the peat components, which are the reason for the absorption of the trace elements. Examinations done to compare the effects of peat-mush baths and water baths have shown that peat components - independent from their thermal effects - are the reason for the occurrence of special effects. This applies in particular to the parameter soluble interleukin-2-receptor. As regards estradiol, a significant increase could be measured after peat-mush baths had been applied to 17 postmenopausal female patients (n=11). Comparing these results with those of the group of patients treated with water baths, we noticed that the increase of estradiol was remarkably lower and not significant. The effect of the peat components is thought to be the reason for this.

Administration, Intravaginal↗

Determination of trace elements in zeolites by laser ablation ICP-MS.

Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation conditions employed (lambda: 266 nm, repetition frequency: 10 Hz, pulse energy: 10 mJ, laser power density: 6 x 10(9) W/cm2) fractionation effects of the determined elements relative to the internal standard element Ti were not observed.

Journal Article↗

Factors involved in trace element metabolic abnormalities in hemodialysis patients.

Hair samples taken from a patient group comprising 28 long-term hemodialysis patients (14 males and 14 females) and a control group comprising the same number of normal humans with the same age, sex, residence region, working region and sampling timing as the patient group were analyzed for 22 elements. These subjects were all free of exposure to any trace element. The results are as follows: 1) The patient group had no difference from the control group in hair Na, K, Ca, P or Mg level, variance or correlation coefficient between two elements. 2) The patient group had significantly higher values of hair Se, Sn, Mo and Cr levels and significantly lower values of hair Fe, Ni, Co, Pb and Cd levels. 3) In the patient group, variances of Se, Sn, Mo, Cr and Sr levels were significantly lower. 4) A significant correlation was found in P-Mo. Mg-Sr, Zn-Fe, Li-Sr, Mo-Sb and Cr-Co in both groups, with a significant difference in correlation coefficient between the two groups. 5) The following four factors, causative of trace element level changes in the patient group, were derived by factor analysis: Factor 1, involved in Ca metabolism, Factor 2, involved in dietary therapy, Factor 3, involved in water metabolism, and Factor 4, involved in an unknown pathologic status based on both chronic renal failure and hemodialysis. 6) Factor analysis revealed abnormal behavior of Sr, Li, Al and V, all of with showed no level changes in the patient group.

Adult↗

The content of trace elements (Cu, Zn, Fe, Mg) in fingernails of children.

The concentrations of Cu, Zn, Fe and Mg in fingernails of 212 normal children, 109 males and 103 females, 6--11 years old, were determined by atomic absorption spectroscopy. A wide scatter of results in all trace element determinations in fingernails was found. Nevertheless, it was noted that the petrographical composition of the region influences the trace element concentration in fingernails. An age variation was observed for Cu and Fe. Nail concentrations of the same trace elements were significantly higher in male than in female children.

Age Factors↗

RESEARCH: Comparison of Temporal Trends in Ambient and Compliance Trace Element and PCB Data in Pool 2 of the Mississippi River, USA, 1985-1995.

/ The Intergovernmental Task Force on Monitoring has suggested studies on ambient (in-stream) and compliance (wastewater) data to determine if monitoring can be reduced locally or nationally. The similarity in temporal trends between retrospective ambient and compliance water-quality data collected from Pool 2 of the Mississippi River, USA, was determined for 1985-1995. Constituents studied included the following trace elements: arsenic (As), cadmium (Cd), chromium (Cr), hexavalent chromium (Cr(6+)), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni), selenium (Se), zinc (Zn), and polychlorinated biphenyls (PCBs). Water-column, bed-sediment, and fish-tissue (fillets) data collected by five government agencies comprised the ambient data set; effluent data from five registered facilities comprised the compliance data set. The nonparametric Mann-Kendall trend test indicated that 33% of temporal trends in all data were statistically significant (P < 0.05). Possible reasons for this were low sample sizes, and a high percentage of samples below the analytical detection limit. Trends in compliance data were more distinct; most trace elements decreased significantly, probably due to improvements in wastewater treatment. Seven trace elements (Cr, Cd, Cu, Pb, Hg, Ni, and Zn) had statistically significant decreases in wastewater and portions of either or both ambient water and bed sediment. No trends were found in fish tissue. Inconsistency in trends between ambient and compliance data were often found for individual constituents, making overall similarity between the data sets difficult to determine. Logistical differences in monitoring programs, such as varying field and laboratory methods among agencies, made it difficult to assess ambient temporal trends.KEY WORDS: Mann-Kendall trend test; Ambient data; Compliance data; Trace elements; PCBs, Mississippi Riverhttp://link.springer-ny.com/link/service/journals/00267/bibs/24n4p497.html</HEA

Journal Article↗

Spectrographic analysis of trace elements in archaeological skeletal material from Florida: a preliminary report.

Technological advances have resulted in the development of an additional approach to determining the dietary practices of prehistoric populations. Bones are known to retain certain trace elements, the analysis of which should yield valuable clues to subsistence. Since there has never been a study of this nature attempted on Indian remains in Florida, a qualitative trace element analysis, using an optical emission spectrograph, was made of bone samples from indigenous populations representing both inland and coastal environments in this region. Results of this study showed that magnesium was present in all samples, copper was present in nearly half the samples, and manganese and zinc were not detected. Thus, although the diets of these groups may have varied, the trace element content did not reflect significant differences as have been reported for other types of analyses on Indian populations from diverse geographic regions.

Bone and Bones↗

Determination of trace elements of Egyptian cane sugar (Naga Hammady factories) by neutron activation, atomic absorption spectrophotometric and inductively coupled plasma-atomic emission spectrometric analyses.

INAA, AAS and ICP-AES techniques are applied to the determination of trace amounts of Ag, Al, As, Au, Ba, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Dy, Eu, Fe, Ga, Hf, K, La, Li, Lu, Mg, Mn, Na, Nb, Ni, Pb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Th, Ti, U, V, W and Zn in the stalks of sugar cane plant after extracting juice, raw juice principal (mixed) juice, juice withdrawn from the successive stages of sugar industry, sirup, deposits from evaporators, molasse, A-? and B-sugar and in the soil samples (collected from the field supplying the factories by cane plants) taken from the immediate vicinity of the plant roots at surface, 30 and 60 cm depth. The results obtained are in a good agreement of the safety baselines of using juice as beverage, molasse derivatives (honey, sweets, ...) as diet for common people in the developed countries and in industry (methanol, ethanol, acetone & acetic acid, ...) and sugar sweeting for many purposes (in beverages, desserts, ...). Differences of trace elements concentrations in soil samples may be reasoned to geochemical and biogeochemical fractionation while those in juice may be due to the changes in the environmental conditions, chemical composition and botanic structures. Variations in trace element contents in the products formed during the successive stages of sugar industry may be a result of evaporation, filtration processes, chemical treatments or corrosion of vessels, containers or engines. Trace elements are very important where they are responsible for enzymatic and biochemical reactions, matabolism, health and diseases.

Carbohydrates↗

Trace element status in healthy subjects switching from a mixed to a lactovegetarian diet for 12 mo.

The consequences of a change from a mixed to a lactovegetarian diet for 12 mo on trace element concentrations in plasma, hair, urine, and feces were studied in 16 women and 4 men. After the diet shift, intakes of zinc and magnesium did not change but that of selenium decreased by 40%. Three months after the diet shift, plasma and hair concentrations of zinc, copper, and selenium had decreased but those of magnesium had increased and the concentrations of mercury, lead, and cadmium in hair were lower. Also, the excretion of zinc, copper, and magnesium in urine, and that of selenium in urine and feces had decreased. Only small changes occurred during the remaining lactovegetarian-diet period. Three years later trace element concentrations had reverted towards baseline concentrations; copper values were similar to baseline concentrations but data for magnesium were slightly higher, and more complex patterns were observed for zinc and selenium. It is concluded that a shift to a lactovegetarian diet changes trace element status.

Adult↗

Alterations of trace elements in kidney, spleen and lungs in treated and untreated experimental liver cirrhosis.

Repeated administration of carbon tetrachloride (CC1(4)) to the experimental animals not only produces liver cirrhosis but also pathological changes in different organs. The alteration of trace elements in the plasma and in the liver has been documented. Very limited studies were carried out regarding the alteration of trace elements in different organs in experimental animals subjected to CC1(4) toxicity and the influence of scavengers such as superoxide dismutase (SOD) and allopurinol as preventative measurements. Four groups of animals were studied: CC1(4) and allopurinol (group 1), CC1(4) and SOD (group 2), CC1(4) alone (group 3) and olive oil (group 4). Analysis of tissue concentrations of trace elements in different organ's tissues (e.g. lung, spleen and kidneys) were performed. Histopathological assessments were studied in all groups after 7 weeks of repeated administration of the solutions. Copper contents in the spleen and lungs were significantly high in group 2, while kidney copper contents were significantly high in all experimental groups. Selenium contents in the kidneys and lungs were significantly low in group 1, while it was significantly high in group 2 in all organs. Manganese contents in kidneys was significantly low in group 1 and significantly increased in group 2 in the case of spleen and lung. Lung zinc content was significantly increased in group 2. Spleen zinc decreased significantly only in group 3. Histopathological assessment indicated evidence of interstitial pneumonia in the group treated with allopurinol. The low levels of selenium predisposes to the development of interstitial pneumonia.

Allopurinol↗

Some analytical problems encountered for trace elements determination in the airborne particulate matter of urban and rural areas.

The determination of trace elements (TE) in airborne particulate matter collected onto filters requires an accurate evaluation of the entire analytical procedure. Since many elements have to be determined at a few milligrams of air dust at nanogram levels, possible sources of error can arise from uncontrolled parameters such as blank of the filters, sample homogeneity, pre-analytical treatment, primary and comparator standards. These potential critical points are presented here and discussed on the basis of the experience developed in our laboratory in previous studies where several TE monitoring campaigns have been performed for air particulate matter collected in urban as well as in rural residential areas of north Italy. Instrumental neutron activation analysis (INAA) and electrothermal atomic absorption spectroscopy (ET-AAS) have been used for the investigation of more than 30 trace elements.

Air Pollution↗

Quantification of trace elements in the brain of SIDS victims.

In this report, the quantification and analysis of trace elements in the frontal lobes of the brains of sudden infant death syndrome (SIDS) cases were carried out. In all materials, V, Cr, Sn and Sb were not observed and Mg, Na, K, Fe, Zn and Br were observed. As for all of these trace elements, there was no significant difference between SIDS and non-SIDS. Only Ca was not observed in SIDS and observed only in non-SIDS. It is well known that Ca moves from outside of cells to inside of cells and induces cell damage by membrane disturbance in a hypoxic situation. The result in this report suggests that the deaths in SIDS cases are so sudden and are not sufficient for the kinetics of Ca into brain cells in the hypoxic situation.

Calcium↗

Adsorption of trace elements from poultry litter by montmorillonite clay.

Poultry litter (PL) is used as fertilizer on agricultural lands because of its high nutrient content. However, the litter also contains trace elements such as As, Cd, Cu, Pb, and Zn. On land application of PL, these trace elements may be absorbed by crops, leach into groundwater, or enter the aquatic system as run-off. The objective of this research was to study the effect of the addition of montmorillonite clay-mineral (CM) in reducing the release of trace elements from PL. Cd, Cu, and Zn showed significant decreases of 29, 34, and 22%, respectively, in PL aqueous leachate (compared with the control-PL without CM) on mixing with 0.05 g CM but no change in As, Co, and Cr concentrations was observed. Lead showed a significant increase in PL aqueous leachate on mixing with 0.2 g CM but Pb concentration was two orders of magnitude less than in CM aqueous leachate alone. On washing, the settled precipitate (PL+CM) in the centrifuge tubes with water (desorption study) most of the adsorbed metals (Cd 85%, Cu 61%, and Zn 100%) were released. The results of this study show that the addition of CM resulted in significant adsorption of Cd and Cu from PL.

Adsorption↗

Reference values for the trace elements copper, manganese, selenium, and zinc in the serum/plasma of children, adolescents, and adults.

Up to now few plasma or serum reference or serum reference values have been available for the assessment of the essential trace element supply status in different age groups covering the whole range of life range. In the present investigation, the concentrations of copper, manganese, selenium, and zinc were determined in the serum of 137 healthy children and in the plasma of 68 blood-donors. The age distribution within these groups ranged from 1 month to 18 years and from 22 to 75 years. The determinations were carried out directly by means of electrothermal atomic absorption spectrophotometry with Zeeman background compensation. The adult plasma reference values (mean +/- 2 SD) were 1.65 +/- 8.6 mumol/1 for copper, 14.3 +/- 11.4 nmol/1 for manganese, 0.80 +/- 0.36 mumol/1 for selenium, and 16.6 +/- mumol/1 for zinc. No correlation between concentration of elements and sex could be established. In the child and adolescent group, the manganese levels exhibited an age-dependent linear decrease (54% of the starting value, slope 0.92, r = 0.4, p < 0.001), the copper and the selenium concentrations, respectively, exhibited an exponential increase (107%, r = 0.59 and 174%, r = 0.61), with the highest value in the age group of 6 to 10 years. Reference ranges are established for 9 different age groups. The results reflect the known physiological data on the trace element content in the tissue of children and their diet. The present study is an important pre-requisite for diagnosis and therapy of trace element deficiencies in all age groups.

Adolescent↗