Distribution Of Trace Element Concentrations Research Articles

Importance of the drying method in crystalline phase formation and metallic elements distribution of glycine complexes

In this work, for the first time, the multi mineral complexes composed of three and four elements FeII, MnII, CuII & ZnII and CuII, MnII & ZnII, respectively) bounded to glycine have been produced to be used as a feed additive for farm animals. To the best of our knowledge, all products were synthesized for the first time as novel compounds containing several transition metals. The impact of the drying procedure on the microstructure, chemical composition and crystalline phase was evaluated using different analytical techniques. The trace element concentration distributions and homogeneity were also studied. A single crystal of dehydrated metal glycinate compound was synthesized from drying of glycine and a multi-metal sulphate solution under room temperature. On the other hand, both spray drying and spray granulation of this similar solution results to the formation of crystalline powders. The crystalline powders obtained present a typical metal-sulphate-glycinate dehydrated crystalline form and a homogeneous distribution of the metals within the product particles. The developed products have been compared and their differences have been underlined.

Geochemistry and Sr, S, and O stable isotopes of Miocene Abu Dhabi evaporites, United Arab Emirates

This study investigates for the first time the subsurface Miocene evaporite facies (Gachsaran Formation) in Abu Dhabi, United Arab Emirates. Forty-five evaporite rock samples were selected for petrographic, mineralogical, and geochemical investigations and stable isotope analyses to decipher their origin and constrain their age. Secondary gypsum with anhydrite relics dominates the investigated evaporitic rocks, with minor amounts of clays, dolomicrite, Fe/Ti oxides, and celestite. These samples are characterized by their excellent purity and low variability in geochemical composition. The distribution of trace element concentrations is significantly influenced by continental detrital intake. The main focus of the study is to determine the strontium, sulfur, and oxygen stable isotope compositions. The measured 87Sr/86Sr values of 0.708411–0.708739 are consistent with Miocene marine sulfates and indicate ∼21.12–15.91 Ma (Late Aquitanian-Burdigalian). The δ34S and δ18O values are 17.10‰–21.59‰ and 11.89‰–19.16‰, respectively. These values are comparable to those of Tertiary marine evaporites. The relatively low values of δ34S suggest that non-marine water possesses little influence on S distribution. The geochemical composition and Sr, S, and O isotope distributions of the Abu Dhabi gypsum facies from the Gachsaran Formation reveals that their source brines were marine (coastal saline/sabkha) with subordinate continental input.

Distribution of trace element concentrations in invertebrate species collected from Tokyo Bay, Japan

Distribution of trace element concentrations in invertebrate species collected from Tokyo Bay, Japan

Spatial distribution of trace elements (As, Cd, Ni, Pb) from PM10 aerosols and human health impact assessment in an Eastern European country, Romania

In the present study, the concentrations of trace elements in PM10 were determined and analyzed at 115 monitoring stations in Romania throughout the period 2009–2018. The spatiotemporal distribution of trace element concentrations of PM10, the source apportionment and health impact assessment, was carried out. The results showed a very high multi-annual mean concentration for PM10 and trace elements as well. The multiannual average concentration of PM10 was higher by 29.75% than the World Health Organization recommendation. All studied air pollutants showed a decreasing trend during the studied years, showing with 17.84%, 50.21%, 43.36%, 11.27%, and 72.09% lower values for PM10, As-, Cd-, Ni-, and Pb-, respectively, due to environmental regulations. To assess the human health impact, the hazard quotient (HQ) and cancer risk (CR) were calculated using the health risk model developed by the US Environmental Protection Agency (EPA). The Cd and Ni might present a non-carcinogenic risk to both adults and children; however, the hazard quotient values are higher than the safe limit, with 9.53 and 1.93, respectively. In addition, our study results revealed that the inhalation of As, Cd and the dermal absorption of all studied trace elements were considered as the most important risk factors for developing cancer, especially in case of adults.

Trace elements of naftides of oil- and gas-bearing basin

The parameters of the concentration distribution of trace elements in the oil fields of oil and gas basins of the world, their physic-chemical properties, as well as the geological and geochemical features of oil formation in these basins were studied. It is shown that the ontogenesis of hydrocarbons associated with deep tectonic transformations (geodynamic factor) controls not only the placement of naphtides in the sedimentary cover, but also the diversity of their metallogenic specialization. The classification of oils of various ontogenesis zones is given in accordance to the degree of their enrichment of mineral elements and their belonging to the vanadium or nickel metallogenic type. The oil, characterized by primary rich concentrations of trace elements of the main zone of oil formation, and oil with initially low concentrations of trace elements in the zones of early generation are presented. The processes of transformation of the composition of oils in the areas of hypergenesis lead to their enrichment, whereas the oil of the catagenesis zone is depleted in trace elements.

Trace element contamination in feather and tissue samples from Anna’s hummingbirds

Trace element contamination (17 elements; Be, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Hg, Tl, and Pb) of live (feather samples only) and deceased (feather and tissue samples) Anna's hummingbirds (Calypte anna) was evaluated. Samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS; 17 elements) and atomic absorption spectrophotometry (Hg only). Mean plus one standard deviation (SD) was considered the benchmark, and concentrations above the mean+1 SD were considered elevated above normal. Contour feathers were sampled from live birds of varying age, sex, and California locations. In order to reduce thermal impacts, minimal feathers were taken from live birds, therefore a novel method was developed for preparation of low mass feather samples for ICP-MS analysis. The study found that the novel feather preparation method enabled small mass feather samples to be analyzed for trace elements using ICP-MS. For feather samples from live birds, all trace elements, with the exception of beryllium, had concentrations above the mean+1 SD. Important risk factors for elevated trace element concentrations in feathers of live birds were age for iron, zinc, and arsenic, and location for iron, manganese, zinc, and selenium. For samples from deceased birds, ICP-MS results from body and tail feathers were correlated for Fe, Zn, and Pb, and feather concentrations were correlated with renal (Fe, Zn, Pb) or hepatic (Hg) tissue concentrations. Results for AA spectrophotometry analyzed samples from deceased birds further supported the ICP-MS findings where a strong correlation between mercury concentrations in feather and tissue (pectoral muscle) samples was found. These study results support that sampling feathers from live free-ranging hummingbirds might be a useful, non-lethal sampling method for evaluating trace element exposure and provides a sampling alternative since their small body size limits traditional sampling of blood and tissues. The results from this study provide a benchmark for the distribution of trace element concentrations in feather and tissue samples from hummingbirds and suggests a reference mark for exceeding normal. Lastly, pollinating avian species are minimally represented in the literature as bioindicators for environmental trace element contamination. Given that trace elements can move through food chains by a variety of routes, our study indicates that hummingbirds are possible bioindicators of environmental trace element contamination.

Material and elemental composition of surface aerosols on the north-western coast of the Kandalaksha Bay of the White Sea

Continuous sampling of aerosols is carried out on the north-western (NW) coast of the Kandalaksha Bay of the White Sea. Aerosol matter from 30 filters collected in summer and autumn, 2013, and spring, 2014, was studied by scanning electron microscopy. The elemental composition of aerosol matter was determined by the inductively-coupled plasma mass-spectrometry (ICP-MS). The major portion of aerosol particles collected in summer is of biogenic origin. Heavy metal concentrations in aerosols are at the Arctic background level. The distribution of trace element concentrations is characterized by simultaneous peaks of different elements. The backward trajectory analysis shows an increase in Ni and Cu concentrations corresponding to the arrival of air masses from the western part of the Kola Peninsula. That suggests the influence of smelters.

On the distribution of trace element concentrations in multiple bone elements in 10 Danish medieval and post-medieval individuals.

The differences in trace element concentrations among 19 different bone elements procured from 10 archaeologically derived human skeletons have been investigated. The 10 individuals are dated archaeologically and some by radiocarbon dating to the medieval and post-medieval period, an interval from ca. AD 1150 to ca. AD 1810. This study is relevant for two reasons. First, most archaeometric studies analyze only one bone sample from each individual; so to what degree are the bones in the human body equal in trace element chemistry? Second, differences in turnover time of the bone elements makes the cortical tissues record the trace element concentrations in equilibrium with the blood stream over a longer time earlier in life than the trabecular. Therefore, any differences in trace element concentrations between the bone elements can yield what can be termed a chemical life history of the individual, revealing changes in diet, provenance, or medication throughout life. Thorough decontamination and strict exclusion of non-viable data has secured a dataset of high quality. The measurements were carried out using Inductively Coupled Plasma Mass Spectrometry (for Fe, Mn, Al, Ca, Mg, Na, Ba, Sr, Zn, Pb and As) and Cold Vapor Atomic Absorption Spectroscopy (for Hg) on ca. 20 mg samples. Twelve major and trace elements have been measured on 19 bone elements from 10 different individuals interred at five cemeteries widely distributed in medieval and renaissance Denmark. The ranges of the concentrations of elements were: Na (2240-5660 µgg-1 ), Mg (440-2490 µgg-1 ), Al (9-2030 µgg-1 ), Ca (22-36 wt. %), Mn (5-11450 µgg-1 ), Fe (32-41850 µgg-1 ), Zn (69-2610 µgg-1 ), As (0.4-120 µgg-1 ), Sr (101-815 µgg-1 ), Ba (8-880 µgg-1 ), Hg (7-78730 ngg-1 ), and Pb (0.8-426 µgg-1 ). It is found that excess As is mainly of diagenetic origin. The results support that Ba and Sr concentrations are effective provenance or dietary indicators. Migrating behavior or changes in diet have been observed in four individuals; non-migratory or non-changing diet in six out of the 10 individuals studied. From the two most mobile (most changing diet) individuals in the study, it is deduced that the fastest turnover is seen in the trabecular tissues of the long bones and the hands and the feet, and that these bone elements have higher turnover rates than centrally placed trabecular bone tissue, such as from the ilium or the spine. Comparing Sr and published bone turnover times, it is concluded that the differences seen in Sr concentrations are not caused by diagenesis, but by changes of diet or provenance. Finally, it is concluded that there can be two viable interpretations of the Pb concentrations, which can either be seen as an indicator for social class or a temporal development of increased Pb exposure over the centuries.

Spatial distribution of trace elements in the surface sediments of a major European estuary (Loire Estuary, France): Source identification and evaluation of anthropogenic contribution

Assessing the extent of metal contamination in estuarine surface sediments is hampered by the high heterogeneity of sediment characteristics, the spatial variability of trace element sources, sedimentary dynamics and geochemical processes in addition to the need of accurate reference values for deciphering natural to anthropogenic contribution. Based on 285 surface sediment samples from the Loire Estuary, the first high-resolution spatial distributions are presented for grain-size, particulate organic carbon (POC) and the eight metals/metalloids identified as priority contaminants (Cd, Zn, Pb, Cu, As, Cr, Ni, Hg) plus Ag (an urban tracer). Grain-size and/or POC are major factors controlling the spatial distribution of trace element concentrations. The V-normalized trace metal concentrations divided by the V-normalized concentrations in the basin geochemical background showed the highest Enrichment Factors for Ag and Hg (EF; up to 34 and 140, respectively). These results suggest a severe contamination in the Loire Estuary for both elements. Intra-estuarine Ag and Hg anomalies were identified by comparison between respective normalized concentrations in the Loire Estuary surface sediments and those measured in the surface sediments at the outlet of the Loire River System (watershed-derived). Anthropogenic intra-estuarine Ag and Hg stocks in the uppermost centimetre of the sediment compared with rough annual fluvial flux estimates suggest that the overall strong Enrichment Factors for Ag (EFAg) and and Hg (EFHg) in the Loire Estuary sediments are mainly due to watershed-derived inputs, highlighting the need of high temporal hydro-geochemical monitoring to establish reliable incoming fluxes. Significant correlations obtained between EFCd and EFAg, EFCu and POC and EFHg and POC revealed common behavior and/or sources. Comparison of trace element concentrations with ecotoxicological indices (Sediment Quality Guidelines) provides first standardized information on the sediment quality in the Loire Estuary. The overall mean Effect Range Median quotients (m-ERM-q) results suggested that the Loire Estuary is mainly characterized by slightly toxic sediments even if ecotoxicological impacts have been previously reported on biota.

Annex 1 to: Trace elements mobility in soils from the hydrothermal area of Nisyros (Greece)

<div class="page" title="Page 1"><div class="layoutArea"><div class="column"><p><span>Nisyros Island, Greece, is a stratovolcano known for its intense hydrothermal activity. On June 2013, during a multidisciplinary field campaign, soil samples were collected in the caldera area to determinate the main mineralogical assemblages and to investigate the distribution of trace element concentrations and the possible relationship to the contribution of fluids of deep origin. Soil samples were analysed with XRD and for the chemical composition of their leachable (deionized water) and pseudo total (microwave digestion) [...]</span></p></div></div></div>

Copper and Zinc Fractionation in Apple Orchard Soil in the Village of Bukevje (Croatia) Using the Revised Four-Step BCR Extraction Procedure

The aim of this study was to establish the fractionation of copper and zinc in a small apple orchard using the revised (four-step) Bureau Communautaire de Référence (BCR) sequential extraction procedure and assess their potential mobility in soil. Soil samples were collected at the depth of 10 cm to 25 cm, sixteen from the orchard and five control samples from a meadow located some 200 m away from the orchard. As the distribution of trace-element concentrations in the control samples was normal, they were used for comparison as background levels. We also determined soil mineralogical composition, carbonate content, soil pH, cation exchange capacity, and soil organic matter. The extraction yields of Cu and Zn from the control soil were lower than from the orchard soil (25% vs. 34% and 47% vs. 52%, respectively), which pointed to natural processes behind metal bonding in the control soil and greater influence of man-made activities in the orchard soil. Compared to control, the orchard soil had significantly higher concentrations of total Cu (P=0.0009), possibly due to the application of Cu-based fungicides. This assumption was further supported by greater speciation variability of Cu than of zinc, which points to different origins of the two, Cu from pesticides and Zn from the parent bedrock. Copper levels significantly better (P=0.01) correlated with the oxidisable fraction of the orchard soil than of control soil. Residual and organically bound copper and zinc constituted the most important fractions in the studied soils. However, the use of Cu-based fungicides in the apple orchard did not impose environmental and health risk from Cu exposure.

Geochemical distribution of trace element concentrations in the vicinity of Boroo gold mine, Selenge Province, Mongolia

The environmental impacts of Boroo gold mine project in Mongolia was evaluated by chemical characterization of trace element concentrations in water, soils and tailing dam sediment samples. The results showed that concentrations of B, Cd, Ni and Se in the water samples were within the accepted levels of the Mongolia water quality standard (MNS4586: 1998). However, the concentrations of Al, As, Cu, Mn, Fe, Pb, U and Zn were higher than the maximum allowable concentration especially in the monitoring and heap leach wells. The average concentrations of As, Cd, Cu, Ni, Pb and Zn in the tailing dam sediment were 4419, 58.5, 56.0, 4.8, 20.6 and 25.7 mg/kg, respectively. Generally, arsenic and heavy metals in the soil samples were within the acceptable concentrations of the soil standard of Mongolia (MNS 5850: 2008). The chemical characterization of As solid phase in tailing dam sediment showed that the majority of As were found in the residual fraction comprising about 74% of total As. Assessing the potential risk to humans, simple bioavailability extraction test was used to estimate bioavailability of arsenic and heavy metals, and the concentrations extracted from tailing dam sediment were; 288.2 mg/kg As, 7.2 mg/kg Cd, 41.1 mg/kg Cu, 13.5 mg/kg Pb, 4.7 mg/kg Ni and 23.5 mg/kg Zn, respectively. From these results, the Boroo gold mine project has presently not significantly impacted the environment, but there is a high probability that it may act as a source of future contamination.

Trace element concentration distributions in breast, lung and colon tissues

The concentrations of Fe, Cu, Zn and Se in cancerous and benign tissues of breast, lung and intestine (colon) have been determined. In the cases when the element concentration has not been determined in all samples the Kaplan–Meier method has been used for the reconstruction of the original concentration distributions and estimation of the true mean concentrations and medians. Finally, the log-rank test has been applied to compare the elemental concentration distributions between cancerous and benign tissues of the same organ, between cancerous tissues and between benign tissues taken from different organs. Comparing benign and malignant neoplastic tissues, statistically significant differences have been found between Fe and Se concentration distributions of breast as well as for Cu and Zn in the case of lung tissues and in the case of colon tissues for Zn. The concentrations of all elements have been found to be statistically different in cancer tissues as well as in benign ones when comparing the different organs, i.e. groups ‘breast–colon’ and ‘breast–lung’. Concentrations of Fe and Cu have been found to be statistically different in lung and colon cancerous tissues. For benign tissues of lung and colon a statistically significant difference has been found only for Zn.

Analysis of elemental concentration censored distributions in breast malignant and breast benign neoplasm tissues

The total reflection X-ray fluorescence method was applied to study the trace element concentrations in human breast malignant and breast benign neoplasm tissues taken from the women who were patients of Holycross Cancer Centre in Kielce (Poland). These investigations were mainly focused on the development of new possibilities of cancer diagnosis and therapy monitoring. This systematic comparative study was based on relatively large (∼ 100) population studied, namely 26 samples of breast malignant and 68 samples of breast benign neoplasm tissues. The concentrations, being in the range from a few ppb to 0.1%, were determined for thirteen elements (from P to Pb). The results were carefully analysed to investigate the concentration distribution of trace elements in the studied samples. The measurements of concentration of trace elements by total reflection X-ray fluorescence were limited, however, by the detection limit of the method. It was observed that for more than 50% of elements determined, the concentrations were not measured in all samples. These incomplete measurements were treated within the statistical concept called left-random censoring and for the estimation of the mean value and median of censored concentration distributions, the Kaplan–Meier estimator was used. For comparison of concentrations in two populations, the log-rank test was applied, which allows to compare the censored total reflection X-ray fluorescence data. Found statistically significant differences are discussed in more details. It is noted that described data analysis procedures should be the standard tool to analyze the censored concentrations of trace elements analysed by X-ray fluorescence methods.

Log-stable concentration distributions of trace elements in biomedical samples

In the present paper, which follows our earlier observation that the asymmetric and long-tailed concentration distributions of trace elements in biomedical samples, measured by the X-ray fluorescence techniques, can be modeled by the log-stable distributions, further specific aspects of this observation are discussed. First, we demonstrate that, typically, for a quite substantial fraction (10–20%) of trace elements studied in different kinds of biomedical samples, the measured concentration distributions are described in fact by the “symmetric” log-stable distributions, i.e. the asymmetric distributions which are described by the symmetric stable distributions. This observation is, in fact, expected for the random multiplicative process, which models the concentration distributions of trace elements in the biomedical samples. The log-stable nature of concentration distribution of trace elements results in several problems of statistical nature, which have to be addressed in XRF data analysis practice. Consequently, in the present paper, the following problems, namely, (i) the estimation of parameters for stable distributions and (ii) the testing of the log-stable nature of the concentration distribution by using the Anderson–Darling ( A 2) test, especially for symmetric stable distributions, are discussed in detail. In particular, the maximum likelihood estimation and Monte Carlo simulation techniques were used, respectively, for estimation of stable distribution parameters and calculation of the critical values for the Anderson–Darling test. The discussed ideas are exemplified by the results of the study of trace element concentration distributions in selected biomedical samples, which were obtained by using the X-ray fluorescence (XRF, TXRF) methods.

Total-reflection X-ray fluorescence studies of trace elements in biomedical samples

Application of the total-reflection X-ray fluorescence (TXRF) analysis in the studies of trace element contents in biomedical samples is discussed in the following aspects: (i) a nature of trace element concentration distributions, (ii) censoring approach to the detection limits, and (iii) a comparison of two sets of censored data. The paper summarizes the recent results achieved in this topics, in particular, the lognormal, or more general logstable, nature of concentration distribution of trace elements, the random left-censoring and the Kaplan–Meier approach accounting for detection limits and, finally, the application of the logrank test to compare the censored concentrations measured for two groups. These new aspects, which are of importance for applications of the TXRF in different fields, are discussed here in the context of TXRF studies of trace element in various samples of medical interest.

Concentration distribution of trace elements: from normal distribution to Lévy flights

The paper discusses a nature of concentration distributions of trace elements in biomedical samples, which were measured by using the X-ray fluorescence techniques (XRF, TXRF). Our earlier observation, that the lognormal distribution well describes the measured concentration distribution is explained here on a more general ground. Particularly, the role of random multiplicative process, which models the concentration distributions of trace elements in biomedical samples, is discussed in detail. It is demonstrated that the lognormal distribution, appearing when the multiplicative process is driven by normal distribution, can be generalized to the so-called log-stable distribution. Such distribution describes the random multiplicative process, which is driven, instead of normal distribution, by more general stable distribution, being known as the Lévy flights. The presented ideas are exemplified by the results of the study of trace element concentration distributions in selected biomedical samples, obtained by using the conventional (XRF) and (TXRF) X-ray fluorescence methods. Particularly, the first observation of log-stable concentration distribution of trace elements is reported and discussed here in detail.

Determination of concentration distribution of trace elements near the detection limit

The results of a numerical simulation, performed to check the validity of a method developed for reconstruction of concentration distributions truncated by the detection limit, are reported in the context of trace element analysis in biomedical samples by total-reflection X-ray fluorescence. This method, by correcting a distribution over the whole range of concentrations in a population of samples, restores a number of measurements reporting results below the detection limit. We show by Monte Carlo simulations, assuming lognormal distributions to describe both the concentrations measured as well as the detection limits in the biomedical samples, that the method developed is accurate to within 5% for most typical situations. Moreover, we demonstrate that the factor limiting the accuracy of the correction is the number of measurements, not the correction procedure itself. We have found in simulations that the reconstruction of a concentration distribution, for a typical population size of N=100, is possible when the concentrations are measured only in 20–30% of samples. On the other hand, we show that by ignoring the truncation of a concentration distribution by the detection limit, the results can be systematically biased by as much as 50%. The method developed is applied to the analysis of trace elements in human breast tissue samples by total-reflection X-ray fluorescence (TXRF). The results are also discussed in terms of the size of the population studied.

Influence of detection limit on the measured concentration distribution of trace elements

AbstractThe concentration distributions of trace elements in large populations (n > 100) of biomedical samples were studied by x‐ray fluorescence spectrometry. For elements, the concentrations of which measured in all samples exceed the detection limit (DL) of the method, the log‐normal distribution was found to describe the data very well. For other elements, measured in only a fraction of the studied population, the observed distributions were truncated by the variable DL level. We demonstrate, however, that by using the information on the distribution of reported detection limits, the original distributions of concentration, and also the detection limits, can be reconstructed from the measured data. This can be done by solving the system of integral equations relating the measured and original distributions of the concentration and the detection limit. The applicability of this method is demonstrated in a comparative study of trace element concentrations in urine samples. Copyright © 2001 John Wiley & Sons, Ltd.

Some aspects of statistical distribution of trace element concentrations in biomedical samples

Concentrations of trace elements in biomedical samples were studied using X-ray fluorescence (XRF), total reflection X-ray fluorescence (TRXRF) and particle-induced X-ray emission (PIXE) methods. Used analytical methods were compared in terms of their detection limits and applicability for studying the trace elements in large populations of biomedical samples. In a result, the XRF and TRXRF methods were selected to be used for the trace element concentration measurements in the urine and woman full-term placenta samples. The measured trace element concentration distributions were found to be strongly asymmetric and described by the logarithmic–normal distribution. Such a distribution is expected for the random sequential process, which realistically models a level of trace elements in studied biomedical samples. The importance and consequences of this finding are discussed, especially in the context of comparison of the concentration measurements in different populations of biomedical samples.