Instrumental neutron activation analysis of rib bone samples and of bone reference materials

The instrumental neutron activation analysis method was used for the determination of trace elements in rib bone samples taken from autopsies of accident victims. The elements Br, Ca, Cl, Cr, Fe, Mg, Mn, Na, P, Sr, Rb, and Zn were determined in cortical tissues by using short and long irradiations with thermal neutron flux of the IEA-R1m nuclear reactor. The reference materials NIST SRM 1400 Bone Ash and NIST SRM 1486 Bone Meal were also analyzed in order to evaluate the precision and the accuracy of the results. It was verified that lyophilization is the most convenient process for drying bone samples because it does not cause any element losses. Comparisons were made between the results obtained for rib samples and the literature values as well as between the results obtained for different ribs from a single individual and for bones from different individuals.     

Vanadium levels in urine and cystine levels in fingernails and hair of exposed and normal persons

Vanadium was determined by radiochemical neutron activation analysis (RNAA) with proven accuracy in urine of workers occupationally exposed to vanadium-rich dust in a vanadium pentoxide production plant, and values in the range of 3.02–762 ng/mL (median 33.0 ng/mL) were found. In a control group consisting of administrative workers of the plant, urinary vanadium levels were found in the range of 1.05–53.4 ng/mL (median 2.53 ng/mL), whereas in an another control group of occupationally nonexposed persons, these values amounted to 0.066–0.489 ng/mL (median 0.212 ng/mL). Accuracy of the results was tested by analysis of reference material IAEA A-13 Animal Blood and NIST SRM-1515 Apple Leaves, and very good agreement was found with literature and the NIST certified values, respectively. Unlike urine, no significant differences were found for cystine levels in fingernails and hair of exposed and control persons.     

Determination of trace elements in porcine brain by inductively coupled plasma-mass spectrometry,electrothermal atomic absorption spectrometry,and instrumental neutron activation analysis

Methods have been developed for the analyses of trace metals in various areas of porcine brains, (temporal, parietal, frontal cortex, both right and left hemispheres). Determinations were carried out using inductively coupled plasma-mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS). The elements investigated were Li, Mn, Cu, Zn, Cd, Hg, and Pb by ICP-MS and Cu, Cd, and Mn by ETAAS. For determination by ICP-MS, a method of standard additions calibration coupled with internal standards was used, and for ETAAS, standard additions calibrations were prepared. The accuracy of all methods was determined using NIST and IAEA certified reference material. A small number of pig brains were analyzed by instrumental neutron activation analysis for Cr, Co, Cs, Fe, Rb, Se, Sc, Sb, and Zn using the comparator method of analysis. Four separate NIST standard reference materials have been used to examine the validity of the comparator method.     

Validation of an optimized method for the determination of iodine in human breast milk by inductively coupled plasma mass spectrometry (ICPMS) after tetramethylammonium hydroxide extraction

In this study a novel method to determine iodine concentrations in human breast milk was developed and validated. The iodine was analyzed by inductively coupled plasma mass spectrometry (ICPMS) following tetramethylammonium hydroxide (TMAH) extraction at 90 °C in disposable polypropylene tubes. While similar approaches have been used previously, this method adopted a shorter extraction time (1 h vs. 3 h) and used antimony (Sb) as the internal standard, which exhibited greater stability in breast milk and milk powder matrices compared to tellurium (Te). Method validation included: defining iodine linearity up to 200 μg L⁻¹; confirming recovery of iodine from NIST 1549 milk powder. A recovery of 94–98% was also achieved for the NIST 1549 milk powder and human breast milk samples spiked with sodium iodide and thyroxine (T4) solutions. The method quantitation limit (MQL) for human breast milk was 1.6 μg L⁻¹. The intra-assay and inter-assay coefficient of variation for the breast milk samples and NIST powder were <1% and <3.5%, respectively. NIST 1549 milk powder, human breast milk samples and calibration standards spiked with the internal standard were all stable for at least 2.5 months after extraction. The results of the validation process confirmed that this newly developed method provides greater accuracy and precision in the assessment of iodine concentrations in human breast milk than previous methods and therefore offers a more reliable approach for assessing iodine concentrations in human breast milk.     

Acquisition of improved reference values for cesium,iodine, strontium,thorium, and uranium in selected NIST reference materials

As part of a study on the ingestion and organ content of some trace elements of importance in radiological protection, additional work has been undertaken to acquire improved reference values for cesium, iodine, strontium, thorium, and uranium in four selected reference materials provided by the US National Institute of Standards and Technology. The materials are SRM-1548 Total Diet, SRM-1548a Typical Diet, SRM-1486 Bone Meal, and RM-8414 Bovine Muscle. A coordinated study was undertaken with the help of seven selected laboratories in five countries. Instrumental and radiochemical neutron activation analysis and inductively coupled plasma-mass spectrometry were the analytical main techniques used.     

Particle-Induced X-ray Emission (PIXE) Analysis of Minor and Trace Elements in Gallstones of Nigerian Patients

Gallstone disease is a major health problem in many parts of the world. In Nigeria, however, only a few cases of gallstone disease are reported. Minor/trace elements are reported to play a significant role in the formation of gallstones. This study was conducted to assess the minor elements in gallstone of Nigerian patients who had cholecystectomy in our institution using particle-induced X-ray emission (PIXE) technique. We also compare the findings with previous reports from outside Nigeria. Fourteen patients who had cholecystectomy for calculous cholecystitis at Obafemi Awolowo University Teaching Hospital Complex, Ile-Ife, Nigeria, between March 2006 and July 2008, had the stone retrieved. The stones were analyzed for trace elements at the Center for Energy Research and Developments of the University using PIXE experiments. Certified standard reference material, NIST 1577a (bovine liver), was equally analyzed to confirm the accuracy of the experimental procedure. Computer code GUPIXWIN was used to analyze the data. Fourteen elements, phosphorus, sulfur, chlorine, potassium, calcium, manganese, iron, copper, zinc, bromide, lead, titanium, rubidium, and strontium, were detected in most of the samples. The concentrations of the elements varied in the different samples, ranging from a few parts per million to a few percent. Ca was the major constituent of all samples. The black sand-like samples had very high levels of P, S, K, and Pb, which were different from a previous report. The distribution of trace elements in stones in Nigeria patients is different from previous report outside Nigeria, and this may have some role in the occurrence of gallstones in the black African.     

The Content of Elements in Infant Formulas and Drinks Against Mineral Requirements of Children

The present study aimed at analysing the content of fluorine (F), calcium (Ca), magnesium (Mg), iron (Fe) and zinc (Zn) in the drinks for children and infant formulas, a popular supplement or substitute for breast milk produced from cow milk on an industrial scale. Ca, Mg, Zn and Fe concentrations were determined using atomic absorption spectrophotometer, while F levels using a potentiometric method. F levels in the examined formula samples increased with the intended age range, until the intended age of 1 year, and then decreased. A lower content of Ca, Mg and Zn was observed in formulas intended for children <1 year of age and higher for older children. Fe content increased with the age range. A statistically significant higher content of Ca, Mg, Zn and Fe in samples intended for children with phenylketonuria in comparison to those intended for healthy children or children with food allergies was noted. The content of the analysed elements in juices and nectars showed the highest contents in products intended for infants (under 6 months of age). The lowest levels of elements tested were found in drinks for children over 6 months of age. In conclusion, the concentrations of the examined elements in infant formulas and juices for children were decidedly greater than the standards for the individual age groups. Although the absorption of these elements from artificial products is far lower than from breast milk, there is still the fear of consequences of excessive concentrations of these minerals.     

Trace element status of hemodialyzed patients

The trace elements Ba, Bi, Cd, Co, Cs, Cu, Hg, La, Mn, Mo, Pb, Rb, Sb, Sn, Sr, Tl, and Zn were determined by inductively coupled plasma mass spectrometry in plasma samples of 68 hemodialysis patients. The same elements (with exception of La and Mn) were also determined in whole blood after mineralization with high-purity nitric acid/hydrogen peroxide in a closed-pressurized microwave system. The accuracy and precision was checked by analyzing two Seronorm “whole blood” reference materials. All samples were contaminated with barium (heparinized tubes) and the plasma samples with tin (collection tubes). The concentrations for Bi, Hg, Pb, Rb, Sb, and Sr in whole blood were within the literature ranges for healthy adults. All of the concentrations for Co, and some of the concentrations for Cd, Cs, Tl, and Zn were higher than the high limits of the normal ranges. Approximately 14% of the Cu concentrations were lower than the low limit of the normal range. The Mo and Sn concentrations are difficult to evaluate, because the normal ranges appears to be unreliable. All concentrations for Cd, Co, Mo, Pb, Sn, and Sr and some of the concentrations for Cu (15%) and Mn (75%) in the plasma samples were higher than the high limits of the normal ranges. The concentrations for Rb tended to be lower than the normal range. To establish unequivocally the causes for elevated and reduced concentrations of trace elements in whole blood and plasma of dialysis patients, all fluids in the dialysis process must be investigated.     

Methodological aspects of moss sample preparation. Effects of freezing and duration of washing on the cellular distribution of elements in Fontinalis squamosa Hedw.

Aquatic bryophytes are widely used in biomonitoring studies, mainly because of their capacity to act as bioaccumulators. As different methods can be used to preserve and process moss samples, the results of elemental analyses may also vary, particularly if the contents of different cellular compartments are analyzed separately. In the present study, we compared the total concentrations of some elements and the concentrations of these in different cellular locations in frozen-thawed and fresh samples of the aquatic moss Fontinalis squamosa that were also washed for different lengths of time before analysis. We used the sequential elution technique (SET) to extract the different fractions, and we determined the concentrations of K, Mg, Ca, Cd, Co, Cu, Al and Zn in the extracts. The results varied depending on the element, cellular location and moss sampling site. In the moss samples processed after freezing, the greatest differences were in the intracellular concentrations of K, Mg and Cd, which were lower than in the fresh samples. Minor differences were found in the concentrations of elements in other cellular locations and in the total concentrations of elements. The increase in the duration of the initial washing step, carried out to remove soluble and particulate intercellular elements, may also cause the release of elements (e.g. K and Mg) bound to extracellular exchange sites. The concentrations in the other cellular fractions and the total concentrations were less affected by the washing duration. Neither freezing nor the use of long washing times are recommended for processing moss samples prior to extraction of elements by the SET. Further studies are needed to confirm and clarify the observations.     

Effects of ambient air particles on nitric oxide production in macrophage cell lines

We assessed the in vitro toxicity of various particles on three murine macrophage cell lines, (J774A.1, WR19M.1, RAW264.7). The cells were exposed to aqueous suspensions (0-100 microg/30 mm2 well) of urban particulate matter (SRM-1648, SRM-1649, EHC-93), fine particulate matter (PM2.5), titanium dioxide (SRM-154b), and respirable cristobalite (SRM-1879) for 2 h and were then stimulated with lipopolysaccharide (LPS, 100 ng/ml) and recombinant interferon-gamma (IFN, 100 U/ml). After overnight incubation with the particles and LPS/IFN, nitric oxide production was estimated from culture supernatant nitrite. Cell viability was determined by monitoring the rate of AlamarBlue reduction. The dose-effect relationships for nitrite and viability were modeled as a power function (Fold change = [Dose+1]beta), where beta represents the slope of the dose-response curve. Potency was defined as the rate of change in nitrite production corrected for cell viability (beta(POTENCY) = beta(NITRITE) - beta(VIABILITY)). Overall, the urban particles decreased nitric oxide production (beta(POTENCY) < 0), while exposure of the cells to fine particulate matter or cristobalite increased the production of nitric oxide (beta(POTENCY) > 0). Titanium dioxide (TiO2) was essentially inactive (beta(POTENCY) approximately to 0). The decrease in nitric oxide production seen in cells exposed to the urban particles was directly correlated to a decrease in the expression of inducible nitric oxide (iNOS) as determined by Western blot analysis. The results indicate that particles are modulators of nitric oxide production in murine macrophages and may directly disrupt expression of iNOS during concomitant pathogen exposure. Pathways leading to enhanced NO production causing cell injury, and to decreased NO release resulting in lower bacterial clearance, may both be relevant to the health effects of ambient particles.     

Reference values for trace and ultratrace elements in human serum determined by double-focusing ICP-MS

Reference values for trace and ultratrace elements concentrations in healthy human serum, measured by double-focusing inductively coupled plasma-mass spectrometry (ICP-MS), are presented. Blood donors from Asturias (Spain) were selected as the reference population (n=59). Blood samples were collected, after donation, taking the necessary precautions to avoid contamination. All subjects analyzed had normal renal function and nutritional status, as shown from their creatinine and albumin levels. A total number of 14 elements (Al, Ca, Cr, Mn, Fe, Co, Cu, Zn, Rb, Sr, Mo, Cd, Pb, and U) were monitored almost simultaneously. Serum samples were diluted 1+4 with ultrapure water and matrix interferences were corrected using Sc, Ga, Y, and Tl as internal standards. Fe, Cu, and Zn were also determined by isotope dilution analysis (IDA). Reference trace element concentrations intervals observed containing 95% of the reference distribution after excluding outliers are presented. Fourteen serum samples from hemodialysis patients were also analyzed for comparison. High levels of Al, Cr, Sr, Mo, Mn, Pb, U, Co, and Cu and low levels of Fe, Zn, and Rb were found in the serum samples from hemodialysis patients compared to the corresponding reference values observed in this work.     

Instrumental neutron activation analysis of Standard Reference Material 1941, Organics in Marine Sediment

The National Institute of Standards and Technology has developed a new Standard Reference Material 1941, “Organics in Marine Sediment.” In addition to the organic constituents, over 30 elements have been determined by instrumental neutron activation analysis and prompt-gamma activation analysis. The homogeneity of the material was investigated and relative standard deviations of single-element concentrations in 250-mg samples were found to be 1% or less with regard to major inorganic constituents and rare earth elements. A slightly higher relative SD was found for elements that may stem from biological or anthropogenic input. The element concentrations determined in this work are discussed in comparison to concentrations in other similar reference materials. Concentrations for 31 elements will be included for information on the certificate.

     

Comparison of Two In Vitro Extraction Protocols for Assessing Metals’ Bioaccessibility Using Dust and Soil Reference Materials

The bioaccessibility of arsenic, cadmium, chromium, copper, lead, nickel, and zinc in four National Institute of Standards and Technology (NIST) standard reference materials and two Canadian dust samples as determined using the Solubility/Bioavailability Research Consortium (SBRC) in vitro procedure ranged from a low of 1.8% for chromium in standard reference material NIST 2711 to a high of 95.2% for cadmium in NIST 2584. The SBRC data were compared to data generated using a modified EN-71 Toy Safety protocol conducted at two different laboratories. Results for the two extraction methods compared well with differences between the means (SBRC vs. modified EN-71) generally less than 10% for the majority of the metals. These differences between the two extraction methods were negligible compared to variability caused by (a) the inherent heterogeneity of typical house dust samples and (b) differences in ICP-MS analytical approaches employed in the different laboratories. Results indicate that the modified EN-71 method is useful and appropriate as a relatively simple, rapid, and reproducible screening test for estimating metals’ bioaccessibility in soil and dust samples.     

Quantitative X-ray microanalysis of halogen elements in biological specimens

Summary Standards were prepared for quantitative X-ray microanalysis of the halogen elements Cl, Br and I in sections of resin embedded biological specimens. Halogenated aromatic compounds were dissolved in resin, which subsequently was polymerized. Homogeneity and stability of the standards were determined and found to be satisfactory. A general procedure of calculation of elemental concentrations according to the continuum method is given for the case that the specimen contains appreciable concentrations of one or more rather heavy elements. It is shown that use of approximations may lead to unacceptable errors, even in the concentration ranges occurring in biological specimens. As a practical application, the concentration of bromine in the chloroplasts of the red alga Chondrus crispus was determined quantitatively. The inner cells contained more bromine than the epidermal cells: in the chloroplasts of the inner cells bromine concentrations of about 6% could be demonstrated.     

Quantitative X-ray microanalysis of halogen elements in biological specimens

Standards were prepared for quantitative X-ray microanalysis of the halogen elements Cl, Br and I in sections of resin embedded biological specimens. Halogenated aromatic compounds were dissolved in resin, which subsequently was polymerized. Homogeneity and stability of the standards were determined and found to be satisfactory. A general procedure of calculation of elemental concentrations according to the continuum method is given for the case that the specimen contains appreciable concentrations of one or more rather heavy elements. It is shown that use of approximations may lead to unacceptable errors, even in the concentration ranges occurring in biological specimens. As a practical application, the concentration of bromine in the chloroplasts of the red alga Chondrus crispus was determined quantitatively. The inner cells contained more bromine than the epidermal cells: in the chloroplasts of the inner cells bromine concentrations of about 6% could be demonstrated.     

Application of inductively coupled plasma sector field mass spectrometry for elemental analysis of urine

An analytical method using double focusing sector field inductively — coupled plasma mass spectrometry (sector field ICPMS) for rapid simultaneous determination of 42 elements in urine is described. Sample preparation consisted of 20-fold dilution with 0.14 mol/l nitric acid in ultrapure water. The importance of controlling possible contamination sources at different sample preparation and analysis stages in order to achieve adequate method detection limits (DL) is emphasized. Correction for matrix effects was made using indium and lutetium as internal standards. Different approaches for accuracy assessment in urine analysis are evaluated. Additional information on trace element concentrations in a urine reference material is given. Between-batch precision was assessed from the analysis of separately prepared aliquots of the reference material and was better than 10% RSD for 32 of the elements. The robustness of the procedure was tested by analysis of about 250 samples in one analytical run lasting more than 50 hours. A statistical summary of results for 19 urine samples from non-exposed subjects is presented. For a majority of the elements tested concentrations were higher than the detection limit of the method.     

Microwave digestion and analysis of foliage for total mercury by cold vapor atomic fluorescence spectroscopy

A microwave technique for digesting foliage samples was developed and evaluated for quantifying low levels of Hg by cold vapor atomic fluorescence spectroscopy, CVAFS. The method meets three criteria: (1) to digest all sample material completely and consistently, (2) to reduce sample digestion time to less than one hour, and (3) to maintain a low analytical blank. Mean recovery of NIST standards was 90±6%. Samples that were analyzed by this technique and by Instrumental Neutron Activation Analysis compared within 15%. This method also compared within 15% of hot acid digestion methods on samples prepared and analyzed by CVAFS at different laboratories in the First International Mercury in Foliage Intercomparison of Methods (FIM)². The largest source of variability in all of the interlaboratory comparisons was sample inhomogeneity rather than analytical error.     

Matrix interferences in the analysis of digested biological tissues with inductively coupled plasma-mass spectrometry

To investigate the physiological roles or toxicity of trace or toxic elements, multielement analysis of limited quantities of samples in the biological tissues is required. Inductively coupled plasma mass spectrometry (ICP-MS) suits this requirement, but spectral and nonspectral interferences are inevitable. We examined correction methods for the nonspectral interferences by analyzing signals of 21 elements in various concentrations of HNO₃ as well as five major elements (Na, K, P, Ca, and Cl). Using internal standards, the interferences caused by the major elements were corrected, but the interferences caused by HNO₃ were impossible to correct for elements with high ionization potentials. The analytical results using the standard addition method on 14 elements in standard reference materials and fresh brain tissues confirmed the accuracy of this method. Thus, we concluded that the standard addition method is useful to correct for the nonspectral interferences.     

Characterization of Soil Contamination in Miduk Mining District,SW Iran

In this study, 30 soil samples were collected from 0–5 cm and 15–20 cm depths in the vicinity of the Miduk Porphyry Copper Mine in Kerman Province, southeast Iran. The samples were analyzed for total concentrations of eight potentially toxic elements. The bioavailability of trace elements is determined using sequential extraction analysis. Average concentrations of As, Cd, Cr, Cu, Mo, Ni, Pb, and Zn in soil samples are 26.9, 0.49, 56.31, 201.18, 1.77, 45.6, 83.87, and 191.94 mg kg^?1, respectively. Also, to assess the bioaccumulation of the analyzed elements, the roots and the leaves of three plant species were sampled and analyzed. The mobility of the analyzed trace elements shows the following decreasing order: Cd > Mo > Ni > Zn > Cu > Cr >Pb> As. The distribution pattern of elements indicates that elemental concentration in Miduk soils is highly influenced by bedrock composition, while soil pollution is mostly affected by ancient mining.     

Determination of concentrations of elements in the atmospheric aerosol of the urban and rural areas of beijing in winter

The proton-induced X-ray emission technique is one of the most suitable methods in the study of the multielement content of atmospheric aerosols. Atmospheric aerosol samples were collected in winter using an eight-stage cascade impactor at a site of the urban center and a rural site of Beijing. The aerosol samples collected were analyzed to determine maximum, minimum, and average concentrations of up to 20 elements and the ratios of the average element concentrations for the coarse to fine particles (C/F) by the PIXE technique. It has been found that the average elemental concentrations in the urban center are higher than those in the rural area, except S and Br. The concentrations for S and Pb in the atmospheric aerosols are found to be less than the results of previous measurement, but their concentrations in the fine particles increased in winter in the samples from the urban center. The deposition probability of the International Commission on Radiological Protection (ICRP) mode and the mass particle-size distributions of the elements determined in the urban center have been utilized to evaluate inhalable particulate matter fractions retained in the three regions of one’s respiratory tract and their harm to human health is discussed.