Selected urinary metal reference concentrations of the Viennese population – urinary metal reference values (Vienna)

Reference concentrations of metals are the basis for risk assessment studies and for estimation of type and magnitude of environmental and occupational exposure. Urine is often used as a specimen for monitoring studies, as it plays an important role in the elimination of various substances from the body and in addition it can be collected easily. Therefore, the urinary levels of seven trace elements (Al, Co, Cr, Mo, Nb, Ni, Ti) were determined by atomic spectrometric methods (ICP-MS and GFAAS) in 100 urine samples of the Viennese population. The obtained creatinine adjusted concentrations (medians) are in μg/g 6.1, 1.5, 1.1, 46.2, 0.4, 0.1, and 8.0 for Al, Co, Cr, Mo, Nb, Ni, and Ti, respectively.     

Twenty-eight element concentrations in mane hair samples of adult riding horses determined by particle-induced X-ray emission

The concentrations of 28 elements (Al, Br, Ca, Cl, Co, Cu, Cr, Fe, Ga, Hg, K, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Rb, S, Se, Si, Sr, Ti, V, Y, and Zn) were measured in mane hair by the particle-induced X-ray emission method. Except for Br, Cl, K, S, and P, the trace element concentrations in mane hair of horses are similar to literature values for human hair. The values obtained are not dependent on the horse's age, breed, and sex and could be used as reference values in the assessment of diseases and nutritional status in equines.     

Interaction of Lead with Calcium,Iron, and Zinc in the Biological Samples of Malnourished Children

There have been few investigations of trace elements in the urine and hair of populations exposed to high levels of arsenic (As) in drinking water. Therefore, concentrations of selected metals in urine and hair samples from a population in a study area where arsenism was endemic and a control area were determined. It was found that the median concentrations of barium (Ba), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), molybdenum (Mo), nickel (Ni), lead (Pb), zinc (Zn), and As in the urine samples from the population in the study area were 3.87, 0.47, 0.50, 61.84, 26.82, 1.33, 128.45, 7.05, 1.10, 233.75, and 339.63 μg/L, respectively. The corresponding values in the urine samples from a population in the control area were 29.08, 0.19, 0.21, 27.77, 10.32, 4.61, 14.01, 2.19, 3.90, 113.92, and 20.28 μg/L, respectively. In the study area, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn excreted in the urine were likely to be mainly derived from drinking water with high levels of arsenic. The median concentrations of Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Zn, and As in the hair samples from the study area were 4.16, 0.03, 0.09, 1.09, 6.54, 1.97, 0.06, 0.53, 1.64, 144.28, and 1.67 mg/kg, respectively. The corresponding values from the control area were 4.76, 0.03, 0.02, 1.41, 8.31, 1.34, 0.07, 0.39, 0.86, 154.58, and 0.29 mg/kg, respectively. Significant positive correlations were observed between As and Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn in the urine in the study area. However, As was not positively associated with these metals in the hair samples. Exposure to high levels of As in drinking water increased the accumulation of Ba and Mn in the hair and the excretion of Cd, Cu, and Mo in the urine in the study area. The population in the study area might experience Cu and Mo deficiencies for an increasing excretion of Cu and Mo.     

Influence of the coat color on the trace elemental status measured by particle-induced x-ray emission in horse hair

The influence of hair color on the trace elemental status in horse's hair has been studied. A current analytical technique such as particle-induced X-ray emission (PIXE) used in this study has provided reliable, rapid, easy, and relatively inexpensive diagnostic methods. Twenty-eight elements (Al, Br, Ca, Cl, Co, Cu, Cr, Fe, Ga, Hg, K, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Rb, S, Se, Si, Sr, Ti, V, Y, and Zn) in mane hair were detected by the PIXE method. The gray hair contains significantly greter amounts of Cu, Ti, and Zn, and lower amounts of Br, Ca, Se, and Sr than those in other colored horse hairs (p<0.05). Those results measured in the horse's hair were similar to those found in human and dog hair. When interpreting a result, it should be kept in mind that hair color, especially gray hair, influences the concentrations of some elements in horse hair.     

背角无齿蚌对养殖池塘底泥释放重金属的净化效果

通过建立微型生态系统, 分析养殖池塘底泥释放重金属的特征及背角无齿蚌(Anodonta woodiana)对底泥释放重金属的净化效果。底泥对Al、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Mo和Pb的最大释放量分别为636、1.5、70.9、34951、10.3、36.9、34.0、53.2、72.4、48.8和3.0 μg·kg-1 dw; 蚌能够对Al、Cr、Mn、Co、Cu、Zn、As和Mo产生净化作用(P<0.05), 最大去除率分别可达到84.7%、98.0%、33.3%、14.3%、23.5%、69.4%、50.0%和13.0%, 响应面优化分析显示养殖密度和处理时间分别为40 只·m-3和24.49 d、25 只·m-3和23.96 d, Al和As去除率可提升至93.8%和60.5%; Al、Cr、Fe、Co、Cu、Zn、As和Mo的净化效果与养殖数量相关, Al、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Mo和Pb的净化效果与处理时间相关, Cr、Co、Ni、Cu和Zn的净化效果与两者交互作用相关(P<0.05)。提示背角无齿蚌有潜力防控池塘底泥重金属污染。     

AM1* parameters for cobalt and nickel

We report the parameterization of AM1* for the elements Co and Ni. The basis sets for both metals contain one set each of s-, p- and d-orbitals. AM1* parameters are now available for H, C, N, O and F (which use the original AM1 parameters), Al, Si, P, S, Cl, Ti, V, Cr, Co, Ni, Cu, Zn, Br, Zr, Mo and I. The performance and typical errors of AM1* are discussed for Co and Ni and compared with available NDDO Hamiltonians.     

Significance of Trace Element Profile of Blood of Persons with Multiple Caries versus Sound Teeth

In order to determine any possible relation between chemical composition of a person’s blood to formation of dental caries, whole blood was analyzed for 35 inorganic elements (Si, Al, Fe, Ca, Mg, K, Mn, Ti, P, Li, Be, B, V, Cr, Co, Ni, Cu, Zn, As, Sr, Y, Nb, Mo, Ag, Cd, Sn, Sb, Ba, La, Ce, W, Pb, Bi, Zr, and F) in the 15 people having sound teeth as well as an equal number of those having multiple caries. The results showed the absence of 13 elements (Si, Al, Mn, Ti, Be, Co, As, Y, Cd, Ba, La, Ce, and Zr) in the blood of both groups. Of the remaining 22 elements, the results of only seven elements (Fe, P, B, V, Sr, Sn, and F) were significantly different between the two groups. The most remarkable finding of this study was significantly decreased amount of phosphorus, strontium, and fluorine and perhaps increased boron in the blood of persons with caries.     

Mineral Composition of Human fascia lata

The mineral composition of pathologically unchanged human fascia lata was examined here using inductively coupled plasma optical emission spectrometry (ICP-OES) method for the first time. The total concentrations of Ag, Al, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Pb, Sr, Ti, V and Zn were simultaneously measured in the tissue secured during autopsy. The age-related changes and between-gender differences in mineral composition of the examined tissue were investigated and discussed.     

Quantification of 26 metals in human urine samples using ICP-MSMS in a random sample collective of an occupational and environmental health care center in Aachen,Germany

Despite several studies on metal exposure in the general population, the knowledge on the background burden of distinct metals is still sparse (e.g. Cu, In, Mn, Pb, Sn, Sr, Ta, Te). While up to date reference values exist for 16 distinct metals as Biological Reference Value (BAR) or the 95th percentile for Al, As, Ba, Be, Cd, Co, Cr, Hg, Li, Mo, Ni, Pt, Sb, Se, Tl and U respectively, the background burden of the general population for the remaining elements is unknown or yet no matter of scientific counselling. We established and validated an inductively coupled plasma triple quadrupole mass spectrometry (ICP-MSMS) human biomonitoring method (HBM), that enabled us to determine 26 metals in urine. Al, As, Ba, Be, Cd, Co, Cu, Ga, Gd, Hg, In, Li, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ta, Te, Tl, V and Zn were analyzed. The method was applied to 88 urine samples collected in the ambulance of the Institute for Occupational, Social and Environmental Medicine (IASU) Aachen, Germany. Patients from two major metal processing companies (steel and copper) and a more heterogenous group of occupational exposed and non-exposed persons were defined and distinguished. HBM data from about 88, in general occupationally unexposed persons against certain metals served as a collective representing the general population in first approximation. For these the 95th percentiles are reported. Significant differences of urinary metal concentrations of the employees of the two metal processing companies compared to the third group were observed among others for Cu, Cr, Ni, Mn and are discussed, thus demonstrating the usefulness of the method for both environmental and occupational purposes.     

Studies on the Characteristic of Element Contents in the Dominant Plant Species of the Three gorges Region in China

The characteristics of the contents of 20 elements (Al, Fe, Mn, Ca, Mg, K, S, Si, P, Cd, Cu, Zn, Ti, Ni, Sr, Mo, Na, B, Cr, V) in 16 plant species collected from the Three Gorges Region in China were investigated. The average contents of Ca, K and Mg were higher than 1 000 μg·g-1, that of Al, P, Si, Fe, S and Mn ranged between 100—1 000 μg·g-1 and Ti, Cu, Ni, Cr, Mo, Cd and V were less than 10 μg·g- 1. The level of Na content was less than that of the reported. The main character of the element contents was of the Ca> K type. The contents of P, S, Ca and K in different plant samples showed a normal distribution pattern, while Al and Mn showed a elements lognormal distribution pattern. Plant species differed greatly in the element contents. On analyzing the coefficient of variation (C. V., % ), Al, Mn, Mg, Ni, Sr and Fe had higher C.V., while the C.V. of K, S, P, Cr, Cd and Cu was less than 60%, and Cu had the lowest C.V. The correlations between Al and Fe, Al and Ti, Al and Cr, A1 and V, Cd and Sr, Cd and Mo, Fe and V, Zn and Cr, Ni and Sr, Mg and Ni, Mo and Sr, Ca and Sr, Cr and Mo, Na and Mg, Na and P, P and S were statistically significant in different plant species. The classification of the 16 plant species and 20 dements by two-way indicator species analysis (TWINSPAN) method may suggest the difference in dement contents of the different plant species.     

Nickel,cobalt, and molybdenum requirement for growth of Methanobacterium thermoautotrophicum

Growth of Methanobacterium thermoautotrophicum on H₂ and CO₂ as sole energy and carbon sources was found to be dependent on Ni, Co, and Mo. At low concentrations of Ni (<100 nM), Co (<10 nM) and Mo (<10 nM) the amount of cells formed was roughly proportional to the amount of transition metal added to the medium; for the formation of 1 g cells (dry weight) approximately 150 nmol NiCl₂, 20 nmol CoCl₂ and 20 nmol Na₂MoO₄ were required. A dependence of growth on Cu, Mn, Zn, Ca, Al, and B could not be demonstrated. Conditions are described under which the bacterium grew exponentially with a doubling time of 1.8 h up to a cell density of 2 g cells (dry weight)/1.     

Characterization of hypoglycemiant plants by total reflection X-ray fluorescence spectrometry

In this work, synchrotron radiation total reflection X-ray fluorescence spectrometry (SRTXRF) was used to determine trace elements in eight hypoglycemiant plants (Trigonella foenum graecum, Panax ginseng, Pfaffia paniculata, Myrcia speciosa, Zea mays, Harpagophytum procumbens, Syzygium jambolona, and Bauhinia forficate). The elements P, K, Ca, Ti, Mn, Fe, Cu, Zn, Rb, and Sr were detected in all medicinal plants investigated, whereas Si, S, Sc, V, Cr, Co, Ni, Se, Nb, Mo, Sn, Sb, Ba, Hg, and Pb were detected only in some of the samples. The concentration of elements in hypoglycemiant plants varied from 0.15 μg/g of Co to 3.0×10⁴ μg/g of K and the mean of experimental limit of detection for these elements were 0.14 and 3.6 μg/g, respectively.     

Assessment of reference values for elements in human hair of urban schoolboys

Hair samples of youngsters (3–15 years of age) from several urban areas of Rome were analyzed to determine the content of 19 minor and trace elements with the aim of assessing Reference Values (RVs). Thirteen essential elements were taken into account, Ca, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Se, V and Zn. On the other hand, Al, As, Cd, Pb, Sr and Ti were also evaluated on the basis of their potential toxicity. Procedures were developed for the collection, storage and pre-analytical treatment of samples. Measurements were performed by inductively coupled plasma atomic emission spectrometry. Subgroups were formed according to age and sex. Significant differences were found for certain elements depending on age and sex. This was the case, e.g., for Ca which showed a mean value of 336 mg/kg for males and of 537 mg/kg for females. The sex-dependent pattern for this element was also apparent when the three age subgroups of 3–6, 7–10 and 11–15 years were compared. The overall RVs obtained (mg/kg) are as follows Al, 10.2; As, 0.09; Ca, 450; Cd, 0.23; Co, 0.67; Cr, 0.99; Cu, 22.1; Fe, 19.0; Mg, 28.0; Mn, 0.35; Mo, 0.43; Ni, 1.49; P, 195; Pb, 7.11; Se, 0.77; Sr, 1.20; Ti, 0.79; V, 1.22; and Zn 150.     

Non-periodic trends in the oxidative dissolution of transition metals by manganese(III) acetate

As part of a study designed to synthesize the proposed high temperature superconductor MoN, molybdenum powder was reacted with manganese(III) acetate and sodium azide in refluxing glacial acetic acid. No MoN was found. Instead, rapid and complete oxidative dissolution of the metal to soluble forms of Mo(VI) were observed. Removal of the azide or replacement of the azide by chloride had no qualitative effect. Other metals were studied and four groups may be discerned: (1) quantitative dissolution in cold, pure acetic acid - Mn, Fe, Co; (2) quantitative dissolution in refluxing Mn(III) solution  Cu, Mo, In, Sn; (3) partial dissolution in refluxing Mn(III) solution  Ni, V; (4) no reaction  Ti, Zr, Nb, Ta, Cr, W, Re, Rh, Ru, and Pt. Use of preformed metal nitrides, e.g. MoN_0.6, and variation of the oxidant, e.g. replacing Mn(III) by Fe(III) or by Co(III), resulted in little qualitative change. Some unsuccessful attempts to explain this include literature periodic trends for transition metal chemistry and Pourbaix's electrochemical ‘thermodynamic and practical nobility scales’ for corrosion by aqueous media.     

Use of adapted Aspergillus niger in the bioleaching of spent refinery processing catalyst

Spent refinery processing catalyst is listed as a hazardous waste; the toxicity characteristic leaching procedure (TCLP) extracts of the catalyst are found to contain heavy metals at concentrations exceeding the regulated levels. In the present investigation, Aspergillus niger was adapted to single metal ions Ni, Mo or Al (at 100-2,000 mg/L in steps of 100mg/L) and then to a mixture of Ni, Mo and Al (at a mass ratio of 1:2:6, as approximately present in the spent catalyst). Adaptation experiments with single metals showed that the fungus could tolerate up to 1,000 mg/L Ni, 1,200 mg/L Mo and 2,000 mg/L Al. In the presence of a mixture of these metals, the fungus was able to tolerate up to 100mg/L Ni, 200mg/L Mo and 600 mg/L Al. One-step bioleaching experiments with 1 wt% spent catalyst (of particle size <37 microm) were carried out using un-adapted and various adapted fungal strains. In contrast to the adapted strains, the un-adapted strain showed no growth in the presence of the catalyst. Ni:Mo:Al-adapted strain was the most efficient in the leaching of metals from the catalyst (at 78.5% Ni, 82.3% Mo and 65.2% Al) over 30 days due to its tolerance to the toxic elements at 1 wt%. More importantly, the Ni:Mo:Al-adapted strain was capable of bioleaching up to 3 wt% spent catalyst. The TCLP extracts of the spent catalyst after bioleaching using the Ni:Mo:Al-adapted strain showed the concentrations of Ni and Mo were well within the regulated levels.     

Trace and mineral elements in royal jelly and homeostatic effects

Royal jelly from Apis mellifera is a highly active natural biological substance and is probably one of the most interesting raw substances in natural product chemistry. Trace elements play a key role in the biomedical activities associated with royal jelly, as these elements have a multitude of known and unknown biological functions. For this reason concentrations of 28 trace (Al, Ba, Sr, Bi, Cd, Hg, Pb, Sn, Te, Tl, W, Sb, Cr, Ni, Ti, V, Co, Mo) and mineral (P, S, Ca, Mg, K, Na, Zn, Fe, Cu, Mn) elements were systematically investigated in botanically and geologically defined royal jelly samples. In addition, concentrations of 14 trace elements were measured in the associated honey samples--honey being the precursor of royal jelly. Concentrations of K, Na, Mg, Ca, P, S, Cu, Fe, Zn, Al, Ba and Sr in royal jelly were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES), while concentrations of Bi, Cd, Hg, Pb, Sn, Te, Tl, W, Sb, Cr, Mn, Ni, Ti, V, Co and Mo in royal jelly were determined by double focusing magnetic sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). In the honey samples, trace and mineral element concentrations strongly depended on botanical and geological origin, and substantial variation was found. In contrast, the concentrations of trace and mineral elements were highly constant in the associated royal jelly samples. The most important results were the homeostatic adjustments of trace and mineral element concentrations in royal jelly. This effect was evidently produced in the endocrine glands of nurse bees, which are adapted for needs of bee larvae. In conclusion, this research yielded a surprising and completely new finding--that royal jelly, as a form of lactation on the insect level, shows the same homeostatic adjustment as mammalian and human breast milk.     

Trace element composition of Ural licorice Glycyrrhiza uralensis Fisch. (Fabaceae Family)

The trace element composition of the subsurface (roots and rhizomes), overground (leaves and stems), and reproductive (bean valves) organs of Glycyrrhiza uralensis Fisch. was determined by synchrotron radiation X-ray fluorescence analysis (SRXFA). Concentrations of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Hg, Pb, Bi, Th, and U were measured. The data obtained were used to estimate the distribution of some elements in samples of various organs of licorice. Glycyrrhiza uralensis is an accumulator of Fe, Mn, Cu, and Co.     

Geochemistry of recent marine sediments in the Bardawil lagoon,northern Sinai,Egypt

The concentrations of major (Al, Fe, Mg, Ti, K and Na) and minor (Ba, Sr, V, Cu, Mn, Cr, Ni, Zn, Pb and Mo) elements as well as carbonate, organic carbon and total nitrogen have been determined in surface sediments collected at 12 stations from the Bardawil lagoon. The aim of the study was to characterize the geochemistry of the sediments in three different environments, the lagoon, the salt pans and the inlet between the lagoon and the Mediterranean Sea. Higher CaCO₃ percentage (53.5–70.5%) were found in the salt pans where biogenic calcareous components and carbonate rock fragments were found in sufficient quantities in the sediment fractions. Based on high C/N ratios, the organic carbon fraction of the Bardawil lagoon surface sediments is clearly dominated by terrigenous material. The distribution of Al, Fe, Mg and Ti are essentially controlled by the mineralogy of the sediments. The ratios of Ba, Sr, Cu, Mn, Pb and Mo to Al are all high in the salt pans and reflect changes in mineralogy and sediment texture.     

Vehicles and Critical Raw Materials: A Sustainability Assessment Using Thermodynamic Rarity

The changing material composition of cars represents a challenge for future recycling of end‐of‐life vehicles (ELVs). Particularly, as current recycling targets are based solely on mass, critical metals increasingly used in cars might be lost during recycling processes, due to their small mass compared to bulk metals such as Fe and Al. We investigate a complementary indicator to material value in passenger vehicles based on exergy. The indicator is called thermodynamic rarity and represents the exergy cost (GJ) needed for producing a given material from bare rock to the market. According to our results, the thermodynamic rarity of critical metals used in cars, in most cases, supersedes that of the bulk metals that are the current focus of ELV recycling. While Fe, Al, and Cu account for more than 90% of the car's metal content, they only represent 60% of the total rarity of a car. In contrast, while Mo, Co, Nb, and Ni account for less than 1% of the car's metal content, their contribution to the car's rarity is larger than 7%. Rarity increases with the electrification level due to the greater amount of critical metals used; specifically, due to an increased use of (1) Al alloys are mainly used in the car's body‐in‐white of electric cars for light‐weighting purposes, (2) Cu in car electronics, and (3) Co, Li, Ni, and rare earth metals (La, Nd, and Pr) in Li‐ion and NiMH batteries.     

AM1* parameters for gold

We report the parameterisation of AM1* for gold. The basis set for gold contains one set each of s-, p- and d-orbitals. AM1* parameters are now available for H, C, N, O and F (which use the original AM1 parameters), Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Zr, Mo, I and Au. The performance and typical errors of AM1* for gold are discussed.