Application of toxicokinetic-toxicodynamic models in the aquatic ecological risk assessment of metals: A review.

The issue of toxic metal pollution is a considerable environmental concern owing to its complex nature, spatial and temporal variability, and susceptibility to environmental factors. Current water quality criteria and ecological risk assessments of metals are based on single-metal toxicity data from short-term, simplified indoor exposure conditions, ignoring the complexity of actual environmental conditions. This results in increased uncertainty in predicting toxic metal toxicity and risk assessment. Using appropriate bioavailability and effect modeling of metals is critical for establishing environmental quality standards and performing risk assessments for metals. Traditional dose-effect models are based on a static statistical relationship and fall short of revealing the bioavailability and effect processes of metals and do not effectively assess ecological impacts under complex exposure conditions. This paper summarizes the toxicokinetic-toxicodynamic (TK-TD) model, which is gaining interest in environmental and ecotoxicological research. The key concepts, and theories of its construction theories, are discussed and the application of the TK-TD model in toxicity prediction and risk assessment of different metals in the aquatic environment, and trends in the development of the TK-TD model are highlighted. The findings of our review prove that the TK-TD model can effectively predict toxic metal toxicity in real time and under complex exposure conditions in the future.

Prosthetic Metals: Release, Metabolism and Toxicity.

The development of metallic joint prostheses has been ongoing for more than a century alongside advancements in hip and knee arthroplasty. Among the materials utilized, the Cobalt-Chromium-Molybdenum (Co-Cr-Mo) and Titanium-Aluminum-Vanadium (Ti-Al-V) alloys are predominant in joint prosthesis construction, predominantly due to their commendable biocompatibility, mechanical strength, and corrosion resistance. Nonetheless, over time, the physical wear, electrochemical corrosion, and inflammation induced by these alloys that occur post-implantation can cause the release of various metallic components. The released metals can then flow and metabolize in vivo, subsequently causing potential local or systemic harm. This review first details joint prosthesis development and acknowledges the release of prosthetic metals. Second, we outline the metallic concentration, biodistribution, and elimination pathways of the released prosthetic metals. Lastly, we discuss the possible organ, cellular, critical biomolecules, and significant signaling pathway toxicities and adverse effects that arise from exposure to these metals.

Diatoms: Miniscule biological entities with immense importance in synthesis of targeted novel bioparticles and biomonitoring.

Diatoms are the most abundant microscopic unicellular protists in natural lotic ecosystems. They are the major component of the producer community in aquatic ecosystems that also play important roles in biostratigraphy, paleoclimatology and overall ecosystem functioning. In recent times as ultrastructural details of diatom frustule has been established, it has become evident that frustule nanoscale structures play a significant role in adsorption and bioaccumulation of heavy metals. Physical processes like bioaccumulation in conjunction with cell surface ligands and functional groups allow diatoms to convert toxic forms of metals to their more utilizable forms. This unique aspect of diatom has been exploited in recent times for the synthesis of novel nanoparticles under in vitro conditions. Moreover, biomonitoring using diatoms is increasingly becoming a preferred choice for assessment of water quality due to their time-integrative characteristic. Although both these aspects include diatom and metal speciation under in vitro and in situ conditions, a comprehensive study addressing both these areas has remained obscure. Thus, the present work aims at integrating the aspects of novel metal particle synthesis and biomonitoring of habitats with diatom as the principal biological entity involved in these processes.

The application prospect of metal/metal oxide nanoparticles in the treatment of osteoarthritis.

The current understanding of osteoarthritis is developing from a mechanical disease caused by cartilage wear to a complex biological response involving inflammation, oxidative stress and other aspects. Nanoparticles are widely used in drug delivery due to its good stability in vivo and cell uptake efficiency. In addition to the above advantages, metal/metal oxide NPs, such as cerium oxide and manganese dioxide, can also simulate the activity of antioxidant enzymes and catalyze the degradation of superoxide anions and hydrogen peroxide. Degrading of metal/metal oxide nanoparticles releases metal ions, which may slow down the progression of osteoarthritis by inhibiting inflammation, promoting cartilage repair and inhibiting cartilage ossification. In present review, we focused on recent research works concerning osteoarthritis treating with metal/metal oxide nanoparticles, and introduced some potential nanoparticles that may have therapeutic effects.

Exposure to metals premixed with microplastics increases toxicity through bioconcentration and impairs antioxidant defense and cholinergic response in a marine mysid.

Coexistence of metals and microplastics (MPs) in aquatic environments represents a growing concern; however, little is known regarding the risks associated with their combined effects. Here, the effects of five metals (As, Cd, Cu, Pb, and Zn), alone or combined with MPs for various premixing durations (30 and 60 days), on the juvenile and adult stages of the marine mysid Neomysis awatschensis were evaluated. The toxicity (50% lethal concentration for 96 h) and bioconcentration of metals premixed with MPs were measured, and their effects on the antioxidant defense and cholinergic systems were examined. Metal toxicity increased with increasing premixing period with MPs, and juveniles were more sensitive to exposure to metals premixed with MPs than adults. Metal bioconcentration in the mysid body increased following co-exposure with MPs. Metals premixed with MPs significantly increased intracellular malondialdehyde content at both stages but decreased glutathione content in juveniles. At both stages, catalase and superoxide dismutase activity was suppressed following co-exposure to metals and MPs, except under the Cu treatment. Moreover, co-exposure inhibited acetylcholinesterase activity at both stages, suggesting cholinergic impairment. Taken together, metals and MPs produce synergistic detrimental effects on marine mysids in a stage-specific manner. Further studies are warranted to elucidate the role of MPs as a vector for contaminants and stimulator of toxicity in aquatic organisms.

Phytoremediation of potentially toxic elements using constructed wetlands in coastal areas with a mining influence.

This paper proposes the use of wetlands as a phytoremediation strategy for areas of mining and maritime influence in the southeast of Spain. Potentially toxic elements (PTEs) tolerant and salinity-resistant macrophytes (Phragmites australis, Juncus effusus and Iris pseudacorus) have been used. The experiment is carried out in an aerobic artificial wetland using representative sediments affected by mining activities in the study area. Selected species were placed in pots containing substrates made with different mixtures of topsoil and/or peat, mining residues (black or yellow sand). After six months, rhizosphere, root and aerial parts were collected. A transfer study of As, Pb, Zn and Cu is performed, determining contents in rhizosphere and plant (aerial and underground part). From these data, the TF and BCF were calculated for each plant in 15 different substrates. The work is complemented by an initial study of scanning electron microscopy (SEM-EDX) of plants. The obtained results indicate a tolerance of the metallophytes to these PTEs, which may favour the obtaining of a naturalized habitat that acts as an effective protective barrier to the ecosystem, that is easy to maintain and that avoid the risk of transfer to the trophic chain. The use of these species can be a complement to the chemical stabilization proposed for the whole area and carried out in experimental plots. Because they are perennial plants, it is necessary to continue with the experiments and obtain results in a longer period of time that allows to evaluate yield and stabilization.

Distribution and bioconcentration of some elements in the edible mushroom Leccinum scabrum from locations in Poland.

The element concentrations in the fruitbodies of Leccinum scabrum from two forested upland sites and one lowland site of different geochemical background were compared to topsoil concentrations. The aim of the study was to establish baseline concentration datasets, gain insight into the species' bioconcentration potential and to assess the impact of anthropogenic factors. The validated methods for analysis include inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and cold-vapor atomic absorption spectroscopy (CV-AAS). Bioinclusion (bioconcentration factor > 1) by L. scabrum was observed for the elements Ag, Cd, Cu, K, Hg, Mn, Na, Mg, P, Rb, and Zn. In contrast, the elements Al, Ba, Ca, Fe, Ni, and Sr as well as the toxic Pb were bioexcluded. Among these elements, the toxic elements Cd and Pb are noteworthy regarding the aspect of human mushroom consumption. The medians of Cd in caps of L. scabrum from the upland sites were in the range of 5.6-6.6 mg kg-1 dm, with a maximum in an individual sample of 14 mg kg-1 dm, which is in the range of concentrations reported previously for polluted soils. Lead concentrations were much lower, with medians in the range of 0.79-1.3 mg kg-1 dm in caps and 0.48-0.59 mg kg-1 dm in stipes. Mineral contents of L. scabrum appear to be the result of a complex interaction of a species' characteristic physiology with local mineral soil geochemistry and with anthropogenic pollution factors.

Improving ATPase and PPase activities, nutrient uptake and growth of salt stressed ajowan plants by salicylic acid and iron-oxide nanoparticles.

KEY MESSAGE: Salicylic acid and iron-oxide nanoparticles alleviated salt toxicity and improved plant growth by stimulating the activities of H+-ATPase and H+-PPase and preventing nutrient imbalance. Two factorial experiments were undertaken in a greenhouse during 2018 and 2019, to evaluate the impacts of SA (1 mM) and nano-Fe2O3 (3 mM) sprays at 7 leaves and flowering stages on vacuolar H+-pumps, growth and essential oil of salt-subjected (0, 4, 8 and 12 dS m-1 NaCl) ajowan plants. Measurements of plant traits were started at about 12 days after the last foliar spray and continued up to maturity. The H+-ATPase and H+-PPase activities and root ATP content were enhanced under low salinity, but higher salinities reduced these parameters. Rising salinity enhanced Na uptake and translocation, endogenous SA and DPPH activity, while reduced K+/Na+ ratio and nutrients uptake, leading to a reduction in plant biomass. Treatment with SA, nano-Fe2O3 and their combination improved H+-pumps activities and ATP content in roots and leaves. The SA-related treatments caused the highest activities of H+-pumps in roots, but Fe-related treatments resulted in the highest activities of these pumps in leaves. Increasing H+-pumps activities reduced sodium uptake and translocation and enhanced nutrients uptake. Foliar treatments, especially SA + nano-Fe2O3 augmented endogenous SA, DPPH activity, and plant growth in salt-stressed plants. Essential oil contents of vegetative and inflorescence organs under severe salinity and seeds under moderate and severe salinities were enhanced. Maximum essential oil was obtained from seeds of SA + nano-Fe2O3-treated plants, which was strongly correlated with endogenous SA and DPPH. Nevertheless, the SA + nano-Fe2O3 was the best treatment for diminishing salt toxicity and improving ajowan plant growth and essential oil production.

Effects of a soil organic amendment on metal allocation of trees for the phytomanagement of mining-impacted soils.

The suitable application of phytomanagement by phytostabilisation using plant tree species in metal-polluted soils requires an assessment of the fate of metals in biological tree compartments. The goal of this work was to evaluate the effect of an urban compost amendment on metal allocation in two evergreen tree species (Pinus halepensis and Tetraclinis articulata) growing in a metal-enriched polluted substrate. A comprehensive characterisation of edaphic parameters and metal speciation was carried out. Plant analyses included metal concentrations in different tree compartments: roots, stems, branches and leaves. The amendment caused a significant increase in plant biomass for both trees, although T. articulata produced 2.5 times more biomass than P. halepensis. The amendment alleviated P deficiency in P. halepensis. This did not occur for the N deficiency detected in T. articulata. The latter showed no effect of the amendment in the allocation of metals, being most of them restricted at the root compartment (> 50%). For P. halepensis, similar behaviour occurred for Cu, Pb and Zn. However, for Cd, the amendment caused its redistribution into pine shoots, probably due to its transport associated with the increased transpiration. Results indicated that T. articulata may be a promising tree species to be used in phytomanagement programs under semiarid climates due to its low metal translocation into shoots and remarkable biomass production under amendment conditions.

Effect of quarry activities on selected biological resources around quarry site within Onigambari forest plantation, Oyo State, Nigeria.

Quarry activities are creating diverse stress on biological resources in the rural areas where most of them are located globally. In this study, the effect of quarry activities on elephant grass (Pennisetum purpureum) leaves and soils around Onigambari Forest Reserve, Oyo State, Nigeria, were investigated. Soil and samples of elephant grass (Pennisetum purpureum) leaves were collected from two different distances from the quarry plant. Samples used as control were collected within the boundary of Cocoa Research Institute of Nigeria (CRIN), Oyo State, Nigeria estate. Samples were analysed using proton-induced X-ray emission, to determine the elements. The physiochemical parameters were also analysed in both soil and leaves samples. The mean concentration of the elements in the soil sample from Site 1 was higher in Mg, Cl, Ca, Ti, Cr, Mn, Fe, Zn and Zr than Site 2 and the control site. While in leaves, similar trend was observed. Cd and Ag were highly enriched.

Metal remediation potential of naturally occurring plants growing on barren fly ash dumps.

The present study aimed to elucidate the remediation potential of visibly dominant, naturally growing plants obtained from an early colonized fly ash dump near a coal-based thermal power station. The vegetation comprised of grasses like Saccharum spontaneum L., Cynodon dactylon (L.) Pers., herbs such as Tephrosia purpurea (L.) Pers., Sida rhombifolia L., Dysphania ambrosioides (L.) Mosyakin & Clemants, Chromolaena odorata (L.) King & H.E. Robins along with tree saplings Butea monosperma (Lam.) Taub. The growth of the vegetation improved the N and P content of the ash. Average metal concentrations (mg kg-1) in the ash samples and plants were in order Mn (345.1) > Zn (63.7) > Ni (29.3) > Cu (16.8) > Cr (9.9) > Pb (1.7) > Cd (0.41) and Cr (58.58) > Zn (52.74) > Mn (39.09) > Cu (10.71) > Ni (7.45) > Pb (5.52) > Cd (0.14), respectively. The plants showed fly ash dump phytostabilization potential and accumulated Cr (80.19-178.11 mg kg-1) above maximum allowable concentrations for plant tissues. Positive correlations were also obtained for metal concentration in plant roots versus fly ash. Saccharum spontaneum showed highest biomass and is the most efficient plant which can be used for the restoration of ash dumps.

Accumulation of trace metals in eggs and hatchlings of Chelonia mydas.

BACKGROUND: The objective of this study was to verify the accumulation of trace metals in eggs and hatchlings of Chelonia mydas, evaluating if metal accumulation is originated from maternal transfer and/or from the incubation environment. Other assessments were also performed, as metal distribution in different tissues (blood, kidney, liver, muscle, and turtle shells) of newly hatched turtles, and genotoxic analysis, to verify possible damages caused by the presence of metals. METHODS: The assessments were carried out by quantifying Cd, Ni, Pb, Mn and Fe in egg sample collected during laying time (eggshells (ELT) and egg content (EC)), eggshells from newly hatched turtles (ENH), hatchlings tissues (H - blood, kidney, liver, muscle, and shell)) (n = 18 for each biological sample - 3 of each nest) and nest sediments (n = 6, one of each nest). Comparative analysis were made between ELT and ENH, as well as between egg content (EC) and the sum of tissue samples from hatchlings, using Mann-Whitney hypothesis test (p < 0,05). The amount of metals in different hatchling was quantified and followed by the Dunn post-test. A principal component analysis (PCA) was also employed. RESULTS: Metals studied were found in all investigated samples. The concentration of a great amount of investigated metals was significantly higher (P=<0.001) in eggshells from ENH than in ELT. An increase in Cd (2.16-fold), Pb (3.47-fold), Fe (6.83-fold) and Mn (195.57-fold) concentration was noticed in ENH. We also observed an increase in Fe (1.59-fold), Mn (1.74-fold) and Ni (1.59-fold) concentration in hatchling, when compared with EC, due to transfer from nest sediments. In relation to the hatchling's tissues, blood was shown to accumulate higher concentrations of Ni and Pb, while shells accumulated more Cd and Fe, and Mn is more associated with liver and kidney. Fe was the highest accumulated metal in both tissues, and muscles presented discrete concentrations of Ni, Mn, and Pb. A mean concentration of 1.25‰ MN was obtained in C. mydas hatchlings, indicating that the accumulation of metals in hatchlings didn't cause toxicology effects. CONCLUSION: Hatchlings accumulate metals through the maternal and sediment transfer, although the levels of metal accumulation were not enough to cause genotoxic damage.

Impacts of elevated pCO2 on Mediterranean mussel (Mytilus galloprovincialis): Metal bioaccumulation, physiological and cellular parameters.

Ocean acidification alters physiology, acid-base balance and metabolic activity in marine animals. Near future elevated pCO2 conditions could be expected to influence the bioaccumulation of metals, feeding rate and immune parameters in marine mussels. To better understand such impairments, a series of laboratory-controlled experiment was conducted by using a model marine mussel, Mytilus galloprovincialis. The mussels were exposed to three pH conditions according to the projected CO2 emissions in the near future (one ambient: 8.10 and two reduced: 7.80 and 7.50). At first, the bioconcentration of Ag and Cd was studied in both juvenile (2.5 cm) and adult (5.1 cm) mussels by using a highly sensitive radiotracer method (110mAg and 109Cd). The uptake and depuration kinetics were followed 21 and 30 days, respectively. The biokinetic experiments demonstrated that the effect of ocean acidification on bioconcentration was metal-specific and size-specific. The uptake, depuration and tissue distribution of 110mAg were not affected by elevated pCO2 in both juvenile and adult mussels, whereas 109Cd uptake significantly increased with decreasing pH in juveniles but not in adults. Regardless of pH, 110mAg accumulated more efficiently in juvenile mussels than adult mussels. After executing the biokinetic experiment, the perturbation was sustained by using the same mussels and the same experimental set-up, which enabled us to determine filtration rate, haemocyte viability, lysosomal membrane stability, circulating cell-free nucleic acids (ccf-NAs) and protein (ccf-protein) levels. The filtration rate and haemocyte viability gradually decreased by increasing pCO2 level, whereas the lysosomal membrane stability, ccf-NAs, and ccf-protein levels remained unchanged in the mussels exposed to elevated pCO2 for eighty-two days. This study suggests that acidified seawater partially shift metal bioaccumulation, physiological and cellular parameters in the mussel Mytilus galloprovincialis.

Demonstrating the Reliability of bio-met for Determining Compliance with Environmental Quality Standards for Metals in Europe.

The importance of considering the bioavailability of metals in understanding and assessing their toxicity in freshwaters has been recognized for many years. Currently, biotic ligand models (BLMs) are being applied for the derivation and implementation of environmental quality standards (EQS) for metals under the Water Framework Directive in Europe. bio-met is a simplified tool that was developed for implementing bioavailability-based EQS for metals in European freshwaters. We demonstrate the reliability of the relationship between the full BLM predictions and the thresholds (hazardous concentration affecting 5% of species [HC5] values) predicted by bio-met in 3 stages, for the metals copper, nickel, and zinc. First, ecotoxicity data for specific species from laboratory tests in natural waters are compared with predictions by the individual species BLMs included in the full BLMs. Second, the site-specific HC5 values predicted by bio-met for the natural waters used for ecotoxicity testing are compared with those provided by the full BLMs. The reliability of both relationships is demonstrated for all 3 metals, with more than 80% of individual species BLM predictions being within a factor of 3 of the experimental results, and 99% of bio-met local HC5 predictions being within a factor of 2 of the full BLM result. Third, using a larger set of European natural waters in addition demonstrates the reliability of bio-met over a broad range of water chemistry conditions. bio-met is therefore an appropriate tool for performing compliance assessments against EQS values in Europe, due to the demonstrated consistency with the toxicity test data. Environ Toxicol Chem 2020;39:2361-2377. © 2020 SETAC.

Trace elements in two particle size fractions of urban soils collected from playgrounds in Bratislava (Slovakia).

Today, it is proven that the contaminated urban soils are hazardous for the human health. Soil substrates of playgrounds call for special research as they are places where children are directly exposed to soil contaminants. Therefore, the objective of this work was to measure the pseudo-total contents and bioaccessibility of several metals and metalloids (As, Bi, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Sn, V, Zn) in two grain sizes (< 150 µm and < 50 µm) of playground soils in Bratislava city (the capital of Slovakia). The content of metal(loid)s in the soils was controlled by a number of factors, with their increased contents (above 75% percentile or higher) at sites influenced by point sources of pollution (industry and agriculture) or at old sites located in the city centre. Cobalt, Cr, Fe, Mn, Ni and V had relatively uniform contents in soils compared to the other elements. As regression modelling with a categorical variable confirmed, the age of urban areas influenced the accumulation of As, Bi, Cd, Cu, Hg, Pb, Sb and Sn in playground soils. Exploratory statistical techniques with compositionally transformed data (principal component analysis, cluster analysis and construction of symmetric coordinates for correlation analysis) divided trace elements into the two main groupings, Co, Cr, Fe, Mn, Ni, V and Bi, Cd, Cu, Hg, Pb, Sb, Sn, Zn. Median concentrations of the elements in smaller soil grains (< 50 µm) were significantly higher than in coarser grains (< 150 µm). Cobalt, Cu, Mn, Pb, Sn and Zn had significantly higher bioaccessible proportions (% of the pseudo-total content) in < 50 µm soil size than in < 150 µm; however, the same order of bioaccessibility was achieved in both grain sizes. The highest bioaccessibility had Cd, Cu, Pb and Zn (~ 40% and more), followed by Co, As, Mn, Sb (18-27%), Hg, Ni, Sn (10-12%) and finally Cr, Fe and V (less than 4%). The hazard index and carcinogenic risk values were higher in < 50 µm than in < 150 µm and significantly decreased in the two soil sizes when the bioaccessibility results were included in the health hazard calculation.

Biocrusts buffer against the accumulation of soil metallic nutrients induced by warming and rainfall reduction.

The availability of metallic nutrients in dryland soils, many of which are essential for the metabolism of soil organisms and vascular plants, may be altered due to climate change-driven increases in aridity. Biocrusts, soil surface communities dominated by lichens, bryophytes and cyanobacteria, are ecosystem engineers known to exert critical functions in dryland ecosystems. However, their role in regulating metallic nutrient availability under climate change is uncertain. Here, we evaluated whether well-developed biocrusts modulate metallic nutrient availability in response to 7 years of experimental warming and rainfall reduction in a Mediterranean dryland located in southeastern Spain. We found increases in the availability of K, Mg, Zn and Na under warming and rainfall exclusion. However, the presence of a well-developed biocrust cover buffered these effects, most likely because its constituents can uptake significant quantities of available metallic nutrients. Our findings suggest that biocrusts, a biotic community prevalent in drylands, exert an important role in preserving and protecting metallic nutrients in dryland soils from leaching and erosion. Therefore, we highlight the need to protect them to mitigate undesired effects of soil degradation driven by climate change in this globally expanding biome.

Influence of Thermal Pollution on the Physiological Conditions and Bioaccumulation of Metals, Metalloids, and Trace Metals in Whitefish (Coregonus lavaretus L.).

The Kola nuclear power plant, which discharges warm water into one of the bays of subarctic Lake Imandra, significantly changes fish habitats. The temperature gradient of the lake is between 2 and 8 °C, which makes it significantly different from the natural temperature of the lake water. The stenothermal cold-water native species (lake whitefish (Coregonus lavaretus L.)), living for more than 40 years under conditions of thermal pollution, has adapted to this stressor. Moreover, this population differs favorably from the population in the natural-temperature environment in terms of its physiological state. Firstly, the hemoglobin concentrations in the fish blood are in the range of the ecological optimum, and secondly, it has a higher somatic growth, as estimated by Fulton's condition factor. One of its main adaptive mechanisms of ion regulation is an intense metabolism of Na due to the high respiratory activity of the whitefish in warmer water. An increased accumulation of Rb and excretion of Se, Mo, and Si are associated more or less with that feature. Under conditions of an increased water temperature, the main metabolic need is due to a deficiency of Se in fish. The intensive metabolism of selenoproteins may involve risks of toxic effects and the bioaccumulation of Hg, As, and Cu in cases of increased existing stressors or the appearance of new ones.

Ecotoxicological assessment after the world's largest tailing dam collapse (Fundão dam, Mariana, Brazil): effects on oribatid mites.

Worldwide, environmental tragedies involving mining dam ruptures have become more frequent. As occurred a few years ago in Brazil (on 5 November 2015, in Minas Gerais state) the Fundão Dam rupture released 60 million m3 of tailings into terrestrial and aquatic ecosystems. Since then, little information on the ecotoxicity of these tailings has been disclosed. In the laboratory, the acute, chronic and bioaccumulation effects of increased Fundão tailing concentrations on oribatid mites (Scheloribates praeincisus) were assessed. Additionally, the bioaccumulation of 11 trace metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn) and the total density of oribatid mites found in the areas contaminated by the Fundão tailings were determined. The percentages of mite survival and reproductive inhibition were higher than 60% and 80%, respectively, in all contaminated areas with the highest concentration (100% mine tailings). Field studies showed an expressive reduction in the total density of oribatids per m-2 (up to 54 times) in the contaminated areas compared with the reference area. Metal accumulations in the field were 5.4 and 3.2 higher (for Ni and Hg, respectively) and up to two times higher (for most metals) than those in the laboratory for 42 days. The mite responses to the Fundão tailings found in this study suggest long-term interference in their biological development. In this sense, we can conclude that the introduction of mine tailings onto soils tended to compromise the functionality of the mites in the ecosystem, which causes imbalances to cascade other organisms of the trophic web.

Advanced Mg, Zn, Sr, Si Multi-Substituted Hydroxyapatites for Bone Regeneration.

PURPOSE: Compositional tailoring is gaining more attention in the development of advanced biomimetic nanomaterials. In this study, we aimed to prepare advanced multi-substituted hydroxyapatites (ms-HAPs), which show similarity with the inorganic phase of bones and might have therapeutic potential for bone regeneration. MATERIALS: Novel nano hydroxyapatites substituted simultaneously with divalent cations: Mg2+ (1.5%), Zn2+ (0.2%), Sr2+ (5% and 10%), and Si (0.2%) as orthosilicate (SiO4 4-) were designed and successfully synthesized for the first time. METHODS: The ms-HAPs were obtained via a wet-chemistry precipitation route without the use of surfactants, which is a safe and ecologically friendly method. The composition of synthesized materials was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The materials were characterized by X-ray powder diffraction (XRD), FT-IR and FT-Raman spectroscopy, BET measurements and by imaging techniques using high-resolution TEM (HR-TEM), FE-SEM coupled with EDX, and atomic force microscopy (AFM). The ion release was measured in water and in simulated body fluid (SBF). RESULTS: Characterization methods confirmed the presence of the unique phase of pure stoichiometric HAP structure and high compositional purity of all synthesized nanomaterials. The doping elements influenced the crystallite size, the crystallinity, lattice parameters, morphology, particle size and shape, specific surface area, and porosity. Results showed a decrease in both nanoparticle size and crystallinity degree, coupled with an increase in specific surface area of these advanced ms-HAP materials, in comparison with pure stoichiometric HAP. The release of biologically important ions was confirmed in different liquid media, both in static and simulated dynamic conditions. CONCLUSION: The incorporation of the four substituting elements into the HAP structure is demonstrated. Synthesized nanostructured ms-HAP materials might inherit the in vivo effects of substituting functional elements and properties of hydroxyapatite for bone healing and regeneration. Results revealed a rational tailoring approach for the design of a next generation of bioactive ms-HAPs as promising candidates for bone regeneration.

Metal(loid) bioaccessibility and children's health risk assessment of soil and indoor dust from rural and urban school and residential areas.

This study focused on the oral bioaccessibility and children health risks of metal(loid)s (As, Cd, Cr, Cu, Ni, Pb and Zn) in soil/indoor dust of school and households from Lanzhou, China. The simple bioaccessibility extraction test method was applied to assess bioaccessibility, and children's health risk was assessed via statistical modeling (hazard quotients, hazard index and incremental lifetime carcinogenic risk). Metal(loid) content and bioaccessibility in indoor dust samples were significantly higher than those in corresponding soil samples (p < 0.05). The order for mean values of bioaccessibility of the elements in soil was as follows: Cd (57.1%) > Zn (44.6%) > Pb (39.9%) > Cu (33.2%) > Ni (12.4%) > Cr (5.3%) > As (4.4%), while for indoor dust, the order was: As (73.0%) > Cd (68.4%) > Pb (63.3%) > Zn (60.4%) > Cu (36.5%) > Ni (25.2%) > Cr (13.6%). The Pearson correlation coefficient showed that metal(loid) bioaccessibility was in general significantly negatively correlated to the Al, Fe and Mn contents. Neither noncarcinogenic nor carcinogenic risks exceeded the tolerance interval for 3-5- and 6-9-year-old children for all elements. They both were mostly attributed to As considering metal(loid)s types and to school indoor dust considering sources. Therefore, maintaining interior sanitation would be an effective measure to reduce the potential health effects of indoor dust on children.