The trace elements distribution embedded in tooth enamel offers a means to study exposure of toxic metals and allows the reconstruction of dietary behaviors. The quantification of most of the elements with a spatial high resolution (~50μm) is routinely achieved using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). However, the lack of a comprehensive framework of trace elements distribution in enamel jeopardizes any endorsed sampling strategy using LA-ICPMS. The present work is an effort to improve our knowledge on this issue. We studied a suite of 22 sectioned teeth with known dietary history, including 12 3rd molars from 12 living individuals and 10 primary teeth from 3 living individuals. Using LA-ICPMS, we measured Ca, Cu, Zn, Ni, Sr, Ba and Pb variations along 2 or 3 rasters from cervical to occlusal enamel. Calcium concentrations are lower in primary than in permanent teeth and do not vary spatially within a tooth suggesting that enamel matures homogeneously before eruption. The Pb/Ca ratio does not vary within tooth enamel and between primary and permanent tooth enamel. The Cu/Ca and Ni/Ca ratios do not vary within tooth enamel but discriminate primary from permanent tooth enamel. The Zn/Ca ratios are higher in permanent than in primary tooth enamel, and increase up to an order of magnitude in the last hundred of microns at the enamel surface. The Sr/Ca and Ba/Ca ratios are higher in permanent than in primary tooth enamel, and decrease from the enamel-dentine junction towards outer enamel in permanent but not in primary tooth enamel. Considering the Ca-normalized intra-tooth variations of Zn, Sr and Ba, we recommend to perform laser ablation rasters along the enamel-dentine junction because this area is likely to retain most of the original and complete chemical information related to individual's life.
- Keywords
- Barium, Laser ablation, Strontium, Tooth enamel, Transition metals,
- MeSH
- Dentin MeSH
- Adult MeSH
- Middle Aged MeSH
- Humans MeSH
- Aged MeSH
- Trace Elements analysis MeSH
- Calcium MeSH
- Dental Enamel chemistry MeSH
- Tooth, Deciduous MeSH
- Tooth MeSH
- Check Tag
- Adult MeSH
- Middle Aged MeSH
- Humans MeSH
- Male MeSH
- Aged MeSH
- Female MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Trace Elements MeSH
- Calcium MeSH
The sustenance of humans and livestock depends on the protection of the soil. Consequently, the pollution of the soil with potentially toxic elements (PTEs) is of great concern to humanity. The objective of this study is to investigate the source apportionment, concentration levels and spatial distribution of PTEs in selected soils in Frýdek-Místek District of the Czech Republic. The total number of soil samples was 70 (topsoil 49 and 21 subsoils) and was analysed using a portable XRF machine. Contamination factor and the pollution index load were used for the assessment and interpreting the pollution and distribution of PTEs in the soils. The inverse distance weighting was used for the spatial evaluation of the PTEs. The results of the analysis showed that the area is composed of low-to-high pollution site. PTEs displayed spatial variation patterns. The average PTE concentration decreases in this Fe > Ti > Ba > Zr > Rb > Sr > Cr > Y>Cu > Ni > Th order for the topsoil and also decreases in this Fe > Ti > Zr > Ba > Rb > Sr > Cr > Y > Cu > Ni > and Th order for the subsoil. These PTEs Cr, Ni, Cu, Rb, Y, Zr, Ba, Th, and Fe were far above the baseline European average value and the World average value level, respectively. The source apportionment showed the dominance of Cr, Ni, Rb, Ti, Th, Zr, Cu, Fe in the topsoil, while the subsoil was dominated by all the PTEs (factor 1 to 6) except Ba. The study concludes that indiscriminate human activities have an enormous effect on soil pollution.
- Keywords
- Contamination degree, European average value, Potentially toxic elements, Soil pollution, Source apportionment, Spatial distribution,
- MeSH
- Risk Assessment MeSH
- Soil Pollutants analysis toxicity MeSH
- Humans MeSH
- Environmental Monitoring MeSH
- Spatial Analysis MeSH
- Soil chemistry MeSH
- Metals, Heavy analysis toxicity MeSH
- Environmental Pollution analysis statistics & numerical data MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- Czech Republic MeSH
- Names of Substances
- Soil Pollutants MeSH
- Soil MeSH
- Metals, Heavy MeSH
Correlative imaging of cutaneous tumors provides additional information to the standard histopathologic examination. However, the joint progress in the establishment of analytical techniques, such as Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in clinical practice is still limited. Their combination provides complementary information as it is also shown in our study in terms of major biotic (Ca, Mg, and P) and trace (Cu and Zn) elements. To elucidate changes in the elemental composition in tumors, we have compiled a set of malignant tumors (Squamous Cell Carcinoma, Basal Cell Carcinoma, Malignant Melanoma, and Epithelioid Angiosarcoma), one benign tumor (Pigmented Nevus) and one healthy-skin sample. The data processing was based on a methodological pipeline involving binary image registration and affine transformation. Thus, our paper brings a feasibility study of a practical methodological concept that enables us to compare LIBS and LA-ICP-MS results despite the mutual spatial distortion of original elemental images. Moreover, we also show that LIBS could be a sufficient pre-screening method even for a larger number of samples according to the speed and reproducibility of the analyses. Whereas LA-ICP-MS could serve as a ground truth and reference technique for preselected samples.
- Keywords
- Digital histopathology, LA-ICP-MS, LIBS, Numerical correlations, Skin tumor,
- MeSH
- Carcinoma, Basal Cell diagnostic imaging MeSH
- Mass Spectrometry methods MeSH
- Laser Therapy MeSH
- Lasers MeSH
- Humans MeSH
- Melanoma diagnostic imaging pathology MeSH
- Skin Neoplasms * diagnostic imaging pathology MeSH
- Nevus, Pigmented diagnostic imaging MeSH
- Spectrum Analysis methods MeSH
- Carcinoma, Squamous Cell diagnostic imaging pathology MeSH
- Trace Elements analysis MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Trace Elements MeSH
The study intended to assess the level of pollution of potential toxic elements (PTEs) at different soil depths and to evaluate the source contribution in agricultural soil. One hundred and two soil samples were collected for both topsoil (51), and the subsoil (51) and the content of PTEs (Cr, Cu, Cd, Mn, Ni, Pb, As and Zn) were determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The concentrations of Zn and Cd in both soil horizons indicated that the current study levels were higher than the upper continental crust (UCC), world average value (WAV), and European average values (EAV). Nonetheless, the concentration values of PTEs such as Mn and Cu for EAV, As, Cu, Mn, and Pb for UCC, and Pb for WAV were lower than the average values of the corresponding PTEs in this study. The single pollution index, enrichment factor, and ecological risk revealed that the pollution level ranged from low to high. The pollution load index, Nemerow pollution index, and risk index all revealed that pollution levels ranged from low to high. The spatial distribution confirmed that pollution levels varied between the horizons; that is, the subsoil was considered slightly more enriched than the topsoil. Principal component analysis identified the PTE source as geogenic (i.e. for Mn, Cu, Ni, Cr) and anthropogenic (i.e. for Pb, Zn, Cd, and As). PTEs were attributed to various sources using enrichment factor-positive matrix factorization (EF-PMF) and positive matrix factorization (PMF), including geogenic (e.g. rock weathering), fertilizer application, steel industry, industrial sewage irrigation, agrochemicals, and metal works. Both receptor models allotted consistent sources for the PTEs. Multiple linear regression analysis was applied to the receptor models (EF-PMF and PMF), and their efficiency was tested and assessed using root-mean-square error (RMSE), mean absolute error (MAE), and R2 accuracy indicators. The validation and accuracy assessment of the receptor models revealed that the EF-PMF receptor model output significantly reduces errors compared with the parent model PMF. Based on the marginal error levels in RMSE and MAE, 7 of the 8 PTEs (As, Cd, Cr, Cu, Ni, Mn, Pb, and Zn) analysed performed better under the EF-PMF receptor model. The EF-PMF receptor model optimizes the efficiency level in source apportionment, reducing errors in determining the proportion contribution of PTEs in each factor. The purpose of building a model is to maximize efficiency while minimizing inaccuracy. The marginal error limitation encountered in the parent model PMF was circumvented by EF-PMF. As a result, EF-PMF is feasible and useful for apparently polluted environments, whether farmland, urban land, or peri-urban land.
- Keywords
- Enrichment factor-positive matrix factorization, Frýdek-Místek District, Multiple linear regression, Potentially toxic elements, Principal component analysis, Spatial distribution,
- MeSH
- Risk Assessment MeSH
- Cadmium analysis MeSH
- Soil Pollutants * analysis MeSH
- Environmental Monitoring methods MeSH
- Lead analysis MeSH
- Soil chemistry MeSH
- Metals, Heavy * analysis MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- China MeSH
- Names of Substances
- Cadmium MeSH
- Soil Pollutants * MeSH
- Lead MeSH
- Soil MeSH
- Metals, Heavy * MeSH
In the past few decades, contamination of urban children's parks (UCPs) with potentially toxic elements (PTEs) has been attracting more and more interest; however, assessment of eco-environmental and child exposure risks particularly in developing countries remains limited. The current study investigated PTE (Cr, Ni, Zn, As, Cd, and Pb) concentrations, potential sources, and their health risk assessment in UCP soils of 12 major cities in Pakistan. The results showed that the mean concentration of Ni exceeded the SEPA-permissible limit in all UCP sites, while other PTEs were found to be within acceptable limits. The soil properties such as pH, electrical conductivity, organic matter, and soil particles size were determined in UCPs soils. The contamination factor and pollution load index results indicated low to moderate pollution levels (CF < 3) and (PLI<1) for all PTEs except Ni in some of the selected cities. Quantile-quantile (Q-Q) plotting determined the normal distribution line for all PTEs in the UCPs. Principal component analysis showed the mixed sources of contamination from industrial emissions, fossil fuel combustion, vehicular emissions, wastewater irrigation, as well as solid waste disposal and natural sources of soil parent materials in all park sites. ANOVA results showed that all the PTEs except Cd had moderate to higher contamination values than the reference site. The risk assessment study revealed that children had high exposure to the selected PTEs via all exposure pathways. The hazard index (HI) mean value (1.82E+00) of Ni for all exposure pathways was greater than 1, while total risk value of Cr (1.00E-03) had exceeded USEPA limit, indicating cancer risk. Consequently, the study of UCPs soils revealed PTEs contamination that could pose a potential health risk to the local population in the studied UCPs regions of Pakistan. Thus, the present study recommends that the influx of PTEs originating from natural and anthropogenic sources should be mitigated and government should implement strict enforcement of environmental regulations and proper management, as well as air quality monitoring guidelines for public health should be strictly adopted to reduce traffic- and industrial emission-related to PTEs in metropolitan areas.
- Keywords
- Contamination level, Potentially toxic elements, Risk assessment, Source apportionment, Urban children's parks,
- MeSH
- Child MeSH
- Risk Assessment MeSH
- Cadmium analysis MeSH
- Soil Pollutants * analysis MeSH
- Humans MeSH
- Urban Population MeSH
- Environmental Monitoring methods MeSH
- Wastewater analysis MeSH
- Soil chemistry MeSH
- Metals, Heavy * analysis MeSH
- Check Tag
- Child MeSH
- Humans MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- China MeSH
- Pakistan MeSH
- Names of Substances
- Cadmium MeSH
- Soil Pollutants * MeSH
- Waste Water MeSH
- Soil MeSH
- Metals, Heavy * MeSH
The manuscript presents a procedure for optimal sample preparation and the mapping of the spatial distribution of metal ions and nanoparticles in plant roots using laser-induced breakdown spectroscopy (LIBS) in a double-pulse configuration (DP LIBS) in orthogonal reheating mode. Two Nd:YAG lasers were used; the first one was an ablation laser (UP-266 MACRO, New Wave, USA) with a wavelength of 266nm, and the second one (Brilliant, Quantel, France), with a fundamental wavelength of 1064nm, was used to reheat the microplasma. Seedlings of Vicia faba were cultivated for 7 days in CuSO4 or AgNO3 solutions with a concentration of 10µmoll-1 or in a solution of silver nanoparticles (AgNPs) with a concentration of 10µmoll-1 of total Ag, and in distilled water as a control. The total contents of the examined metals in the roots after sample mineralization as well as changes in the concentrations of the metals in the cultivation solutions were monitored by ICP-OES. Root samples embedded in the TissueTek medium and cut into 40µm thick cross sections using the Cryo-Cut Microtome proved to be best suited for an accurate LIBS analysis with a 50µm spatial resolution. 2D raster maps of elemental distribution were created for the emission lines of Cu(I) at 324.754nm and Ag(I) at 328.068nm. The limits of detection of DP LIBS for the root cross sections were estimated to be 4pg for Cu, 18pg for Ag, and 3pg for AgNPs. The results of Ag spatial distribution mapping indicated that unlike Ag+ ions, AgNPs do not penetrate into the inner tissues of Vicia faba roots but stay in their outermost layers. The content of Ag in roots cultivated in the AgNP solution was one order of magnitude lower compared to roots cultivated in the metal ion solutions. The significantly smaller concentration of Ag in root tissues cultivated in the AgNP solution also supports the conclusion that the absorption and uptake of AgNPs by roots of Vicia faba is very slow. LIBS mapping of root sections represents a fast analytical method with sufficient precision and spatial resolution that can provide very important information for researchers, particularly in the fields of plant science and ecotoxicology.
- Keywords
- Distribution, Laser-induced breakdown spectroscopy, Root tissues, Silver nanoparticles,
- MeSH
- Plant Roots metabolism MeSH
- Metal Nanoparticles chemistry MeSH
- Lasers * MeSH
- Copper metabolism MeSH
- Spectrum Analysis * MeSH
- Silver chemistry metabolism MeSH
- Vicia faba metabolism MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Copper MeSH
- Silver MeSH
Fluorescence in situ hybridization (FISH) combined with high-resolution cytometry was used to determine the topographic characteristics of the centromeric heterochromatin (of the chromosomes 6, 8, 9, 17) and the tumor suppressor gene TP53 (which is located on chromosome 17) in cells of the human leukemia cell lines ML-1 and U937. Analysis was performed on cells that were either untreated or irradiated with gamma rays and incubated for different intervals after exposure. Compared to untreated cells, homologous centromeres and the TP53 genes were found closer to each other and also closer to the nuclear center 2 h after irradiation. The spatial relationship between genetic elements returned to that of the unirradiated controls during the next 2-3 h. Statistical evaluation of our experimental results shows that homologous centromeres and the homologous genes are positioned closer to each other 2 h after irradiation because they are localized closer to the center of the nucleus (probably due to more pronounced decondensation of the chromatin related to repair). This radial movement of genetic loci, however, is not connected with repair of DSBs by processes involving homologous recombination, because the angular distribution of homologous sequences remains random after irradiation.
- MeSH
- Cell Nucleus chemistry radiation effects ultrastructure MeSH
- Centromere chemistry radiation effects ultrastructure MeSH
- Genes radiation effects MeSH
- Heterochromatin chemistry radiation effects ultrastructure MeSH
- In Situ Hybridization, Fluorescence MeSH
- Leukemia genetics pathology MeSH
- Humans MeSH
- Chromosomes, Human chemistry radiation effects ultrastructure MeSH
- Neoplastic Stem Cells chemistry radiation effects ultrastructure MeSH
- DNA Repair MeSH
- Image Processing, Computer-Assisted MeSH
- DNA Damage MeSH
- Recombination, Genetic MeSH
- U937 Cells chemistry radiation effects ultrastructure MeSH
- Gamma Rays MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Names of Substances
- Heterochromatin MeSH
Spatial patterns, cluster or dispersion trends are statistically different from random patterns of trace elements (TEs), which are essential to recognize, e.g., how they are distributed and change their behavior in different environmental processes and/or in the polluted/contaminated areas caused by urban and industrial pollutant located in upstream basins and/or by different natural geological conditions. The present study focused on a statistical approach to obtain the spatial variability of TEs (As, B and Sb) in shallow groundwater (GW) in a high-altitude arid region (Lower Katari Basin, Bolivian Altiplano), using multivariate analysis (PCA and HCA), geochemical modeling (PHREEQC, MINTEQ) and spatial analyses (Moran's I and LISA), considering the community supply wells. The results indicate that despite of the outliers there is a good autocorrelation in all cases, since Moran's I values are positive. The global spatial dependence analysis indicated a positive and statistically significant spatial autocorrelation (SA) for all cases and TEs are not randomly distributed at 99% confidence level. The results of hydrochemical modeling suggested the precipitation and stability of Fe (III) phases such as goethite. The re-adsorption of As and Sb on the mineral surface in the aquifer could be limiting the concentrations of both metalloids in southern regions. Spatial autocorrelation was positive (High-High) in northwestern (arsenic), southeastern (boron) and northeastern (antimony) region. The results reflected that the As and Sb are the main pollutants linked to the natural geological conditions, but B is a main pollutant due to the anthropogenic activities. Furthermore, >50% shallow groundwater exceeded the WHO limit and NB-512 guideline values for Sb (87%), B (56%) and As (50%); therefore the spatial distribution and concentrations of these TEs in GW raise a significant concern about drinking water quality in the study area.
- Keywords
- Bolivia, Groundwater, Hydrochemistry, Lower Katari Basin, Spatial variability, Trace elements,
- Publication type
- Journal Article MeSH
A healthy soil is a healthy ecosystem because humans, animals, plants, and water highly depend upon it. Soil pollution by potentially toxic elements (PTEs) is a serious concern for humankind. The study is aimed at (i) assessing the concentrations of PTEs in soils under a long-term heavily industrialized region for coal and textiles, (ii) modeling and mapping the spatial and vertical distributions of PTEs using a GIS-based ordinary kriging technique, and (iii) identifying the possible sources of these PTEs in the Jizerské Mountains (Jizera Mts.) using a positive matrix factorization (PMF) model. Four hundred and forty-two (442) soil samples were analyzed by applying the aqua regia method. To assess the PTE contents, the level of pollution, and the distribution pattern in soil, the contamination factor (CF) and the pollution load index load (PLI) were applied. ArcGIS-based ordinary kriging interpolation was used for the spatial analysis of PTEs. The results of the analysis revealed that the variation in the coefficient (CV) of PTEs in the organic soil was highest in Cr (96.36%), followed by Cu (54.94%) and Pb (49.40%). On the other hand, the mineral soil had Cu (96.88%), Cr (66.70%), and Pb (64.48%) as the highest in CV. The PTEs in both the organic soil and the mineral soil revealed a high heterogeneous variability. Though the study area lies within the "Black Triangle", which is a historic industrial site in Central Europe, this result did not show a substantial influence of the contamination of PTEs in the area. In spite of the rate of pollution in this area being very low based on the findings, there may be a need for intermittent assessment of the soil. This helps to curtail any excessive accumulation and escalation in future. The results may serve as baseline information for pollution assessment. It might support policy-developers in sustainable farming and forestry for the health of an ecosystem towards food security, forest safety, as well as animal and human welfare.
- Keywords
- GIS-kriging, contamination factor, heavy metals, pollution load index, positive matrix factorization,
- Publication type
- Journal Article MeSH
Human activities are altering the fundamental geography of biogeochemicals. Yet we lack an understanding of how the spatial patterns in organismal stoichiometry affect biogeochemical processes and the tools to predict the impacts of global changes on biogeochemical processes. In this contribution we develop stoichiometric distribution models (StDMs), which allow us to map spatial structure in resource elemental composition across a landscape and evaluate spatial responses of consumers. We parameterise StDMs for a consumer-resource (moose-white birch) system and demonstrate that we can develop predictive models of resource stoichiometry across a landscape and that such models could improve our predictions of consumer space use. With results from our study system application, we argue that explicit consideration of the spatial patterns in organismal elemental composition may uncover emergent individual, population, community and ecosystem properties that are not revealed at the local extents routinely used in ecological stoichiometry. We discuss perspectives for further developments and application of StDMs to advance three emerging frameworks for spatial ecosystem ecology in an era of global change; meta-ecosystem theory, macroecological stoichiometry and remotely sensed biogeochemistry. Progress on these emerging frameworks will allow for the integration of ecological stoichiometry and individual space use and fitness.
- Keywords
- Ecosystem ecology, food web, meta-ecosystem, nutrient cycling, nutritional ecology, resource selection, species distribution models,
- MeSH
- Models, Biological MeSH
- Ecology * MeSH
- Ecosystem * MeSH
- Humans MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
