Synthesis of vitamin E and aliphatic lipid vanadium(IV) and (V) complexes, and their cytotoxic properties.

Novel vitamin E chelate derivatives and their VIV/V complexes have been synthesized and characterized, and their anticancer properties have been evaluated. The new complexes have been designed to exhibit enhanced cytotoxicity by combining high lipophilicity with the properties of vanadium to induce the formation of reactive oxygen species (ROS). In particular, the ß-tocopherol derivatives with iminodiethanol (ß-tocDEA) and dipicolylamine (ß-tocDPA) as well their VV and VIV complexes, [VVO(ß-tocDEA] and [VIVO(ß-tocDPA] have been synthesized and characterized by Nuclear Magnetic Resonance (NMR), Ultra Violet-Visible (UV-Vis) and Electron Paramagnetic Resonance (EPR) spectroscopies. Although the ß-tocopherol compounds exhibit antioxidant activity their complexes induce formation of radicals. In addition, two vanadium amphiphilic complexes of 2,2'-((2-hydroxyoctadecyl)azanediyl)bis(ethan-1-ol) (C18DEA) and 1-(bis(pyridin-2-ylmethyl)amino)octadecan-2-ol (C18DPA) known to activate O2 and produce ROS were synthesized and characterized (C. Drouza, A. Dieronitou, I. Hadjiadamou, M. Stylianou, J. Agric. Food. Chem., vol. 65, 2017, pp. 4942-4951). The four amphiphilic vanadium complexes exhibit enhanced hydrolytic stability. All compounds found to be cytotoxic for cancer cells exhibiting activity similar or higher to cis-platin.

Response to vanadate exposure in Ochrobactrum tritici strains.

Vanadium is a transition metal that has been added recently to the EU list of Raw Critical Metals. The growing needs of vanadium primarily in the steel industry justify its increasing economic value. However, because mining of vanadium sources (i. e. ores, concentrates and vanadiferous slags) is expanding, so is vanadium environmental contamination. Bioleaching comes forth as smart strategy to deal with supply demand and environmental contamination. It requires organisms that are able to mobilize the metal and at the same time are resistant to the leachate generated. Here, we investigated the molecular mechanisms underlying vanadium resistance in Ochrobactrum tritici strains. The highly resistant strain 5bvl1 was able to grow at concentrations > 30 mM vanadate, while the O. tritici type strain only tolerated < 3 mM vanadate concentrations. Screening of O. tritici single mutants (chrA, chrC, chrF and recA) growth during vanadate exposure revealed that vanadate resistance was associated with chromate resistance mechanisms (in particular ChrA, an efflux pump and ChrC, a superoxide dismutase). We also showed that sensitivity to vanadate was correlated with increased accumulation of vanadate intracellularly, while in resistant cells this was not found. Other up-regulated proteins found during vanadate exposure were ABC transporters for methionine and iron, suggesting that cellular responses to vanadate toxicity may also induce changes in unspecific transport and chelation of vanadate.

Potential use of Bacillus genera for metals removal from spent catalysts.

The aim of the present study was to isolate microorganisms able to tolerate Ni2+ and V5+ from different sites located close to a mineral mine in Guanajuato, Mexico, and then to evaluate their ability to remove metals contained in a spent catalyst. Seventeen isolates were obtained; among them seven presented a minimum inhibitory concentration (MIC) higher than 200 mg/L of Ni2+ and V5+ each. Nickel and Vanadium removal was evaluated in 9 K liquid medium added with spent catalyst at 16% (s/v) pulp density and incubated at 30 °C, 150 rpm for 7 days. Only three isolates which were coded as PRGSd-MS-2, MNSH2-AH-3, and MNSS-AH-4 showed a significant removal at the end of treatment corresponding in mg kg-1 (or percentage metal removal) of 138 (32%), 123 (29%), and 101 (24%) for Ni, respectively; and 557 (26%), 737 (34%), and 456 (21%) mg kg-1 for V, respectively. The same isolates were capable to remove also Al, Fe, As, and Mg at different extent. Cell morphology changes were observed, in comparison to the control system at the end of biological treatment as a higher quantity of spores for MNSH2-AH-3, 2 µm cells in pairs for MNSS-AH-4, also long chain-vegetative cells having inclusions into the cell surface were observed for PRGSd-MS-2. The three isolated microorganisms were identified by sequencing of the 16S gene as Bacillus thuringiensis, Bacillus megaterium, and Bacillus sp, respectively, suggesting its potential use in the treatment of this solid industrial waste.

Multi-step column leaching using low-molecular-weight organic acids for remediating vanadium- and chromium-contaminated soil.

In soil, vanadium (V) contamination is commonly concomitant with chromium (Cr) contamination, which poses potential risks to humans, animals, and plants due to the transfer of toxic metals and the increase in their concentrations via the food chain or through direct exposure. This study applied a multi-step column leaching process using low-molecular-weight organic acids (LMWOAs) to treat V-contaminated soil from a smelter site that contains 2015.1 mg V kg-1 and 1060.3 mg Cr kg-1. After leaching three times with an equivalent solution/soil ratio of 0.3 mL/g using 1.0 M oxalic acid solution, the total removal rates reached 77.2% and 7.2% for V and Cr, respectively, while the removal rates of the extractable fractions reached 118.6% and 99.2% due to the reduction in residual fraction (F4) of toxic metals. Simultaneously, the distribution and redistribution of geochemical fractions of V and Cr were determined with a sequential extraction technique, and the greater proportion of potential mobile fractions of V (65.1%) may increase its leaching from soil relative to Cr (7.1%). In addition, a lower pH of the leaching agent increased the efficiency of the leaching process to an extent. Compared with batch extraction with a typical solution to soil ratio of 10 mL/g, multi-step column leaching used less agent and hence produced less wastewater. This strategy could reduce the mobilization and bioavailability of toxic metals, and potentially enhance in situ soil flushing for the remediation of V- and Cr- contaminated soil.

Oral bioaccessibility and health risk assessment of vanadium(IV) and vanadium(V) in a vanadium titanomagnetite mining region by a whole digestive system in-vitro method (WDSM).

Oral bioaccessibility of vanadium(IV) and vanadium(V) in soil, dust and concentrate fines from a vanadium titanomagnetite mining region was assessed by a whole digestive system in-vitro scheme. The scheme including the addition of sweat and the large intestinal digestion was used to estimate the oral bioaccessibility of vanadium(IV) and vanadium(V) in the whole digestive system for the first time. Higher oral bioaccessibility of vanadium(IV) and vanadium(V) was determined in gastric and small intestinal phases demonstrating that their major roles for vanadium digestion and absorption. The decreasing order of the oral bioaccessibility of vanadium(IV) and vanadium(V) in each digestive phase was stomach, small intestine, large intestine and mouth. Higher oral bioaccessibility of vanadium(V) in the whole digestion indicated its higher risk potential for human than vanadium(IV). Lower oral bioaccessibility of vanadium(IV) and vanadium(V) determined in bionic digestion illustrated detoxicity potential of human body for ingested vanadium. Compared with soil and dust, higher digestion rate of vanadium in vanadium titanomagnetite concentrate fines indicated its higher risk for human, especially for mining workers. Based on vanadium oral bioaccessibility, hazard quotients of the vanadium were much less than the critical level suggested for no non-carcinogenic risks to the populations surrounding the sampling sites. Indeed, compared with the estimations based on total vanadium content, the incorporation of oral vanadium bioaccessibility into risk assessments could give more realistic information.

Vanadium in Biosphere and Its Role in Biological Processes.

Ultra-trace elements or occasionally beneficial elements (OBE) are the new categories of minerals including vanadium (V). The importance of V is attributed due to its multifaceted biological roles, i.e., glucose and lipid metabolism as an insulin-mimetic, antilipemic and a potent stress alleviating agent in diabetes when vanadium is administered at lower doses. It competes with iron for transferrin (binding site for transportation) and with lactoferrin as it is secreted in milk also. The intracellular enzyme protein tyrosine phosphatase, causing the dephosphorylation at beta subunit of the insulin receptor, is inhibited by vanadium, thus facilitating the uptake of glucose inside the cell but only in the presence of insulin. Vanadium could be useful as a potential immune-stimulating agent and also as an antiinflammatory therapeutic metallodrug targeting various diseases. Physiological state and dose of vanadium compounds hold importance in causing toxicity also. Research has been carried out mostly on laboratory animals but evidence for vanadium importance as a therapeutic agent are available in humans and large animals also. This review examines the potential biochemical and molecular role, possible kinetics and distribution, essentiality, immunity, and toxicity-related study of vanadium in a biological system.

Biokinetic models for Group VB elements.

This paper reviews biokinetic data for the Group VB elements vanadium, niobium, and tantalum, and presents biokinetic models describing their systemic behaviour. The model for systemic niobium in adults was developed earlier and described in Publication 134 of the International Commission on Radiological Protection. The model for niobium is used as a starting point for the development of models for vanadium and tantalum. Published biokinetic data for vanadium, including comparisons with niobium, indicate that the initial distribution of vanadium is broadly similar to that of niobium but that vanadium is less firmly fixed in most tissues and is excreted more rapidly than niobium. Biokinetic data for tantalum are more limited but suggest that its systemic behaviour closely resembles that of niobium at early times after administration. The model for niobium is proposed for application to tantalum in view of the suggested biological similarities of tantalum and niobium, their generally strong coherence in nature due to similar ionic radii and identical valence states, and the difficulties in developing parameter values directly from available data for tantalum. The proposed model for vanadium relies largely on vanadium-specific information and varies considerably from the model for niobium.

Oxidative Stress as a Mechanism Involved in Kidney Damage After Subchronic Exposure to Vanadium Inhalation and Oral Sweetened Beverages in a Mouse Model.

Kidney diseases have notably increased in the last few years. This is partially explained by the increase in metabolic syndrome, diabetes, and systemic blood hypertension. However, there is a segment of the population that has neither of the previous risk factors, yet suffers kidney damage. Exposure to atmospheric pollutants has been suggested as a possible risk factor. Air-suspended particles carry on their surface a variety of fuel combustion-related residues such as metals, and vanadium is one of these. Vanadium might produce oxidative stress resulting in the damage of some organs such as the kidney. Additionally, in countries like Mexico, the ingestion of sweetened beverages is a major issue; whether these beverages alone are responsible for direct kidney damage or whether their ingestion promotes the progression of an existing renal damage generates controversy. In this study, we report the combined effect of vanadium inhalation and sweetened beverages ingestion in a mouse model. Forty CD-1 male mice were distributed in 4 groups: control, vanadium inhalation, 30% sucrose in drinking water, and vanadium inhalation plus sucrose 30% in drinking water. Our results support that vanadium inhalation and the ingestion of 30% sucrose induce functional and histological kidney damage and an increase in oxidative stress biomarkers, which were higher in the combined effect of vanadium plus 30% sucrose. The results also support that the ingestion of 30% sucrose alone without hyperglycemia also produces kidney damage.

Comparison of distribution and toxicity following repeated oral dosing of different vanadium oxide nanoparticles in mice.

Vanadium is an important ultra-trace element derived from fuel product combustion. With the development of nanotechnology, vanadium oxide nanoparticles (VO NPs) have been considered for application in various fields, thus the possibility of release into the environment and human exposure is also increasing. Considering that verification of bioaccumulation and relevant biological responses are essential for safe application of products, in this study, we aimed to identify the physicochemical properties that determine their health effects by comparing the biological effects and tissue distribution of different types of VO NPs in mice. For this, we prepared five types of VO NPs, commercial (C)-VO2 and -V2O5 NPs and synthetic (S)-VO2, -V2O3, and -V2O5 NPs. While the hydrodynamic diameter of the two types of C-VO NPs was irregular and impossible to measure, those of the three types of S-VO NPs was in the range of 125-170nm. The S- and C-V2O5 NPs showed higher dissolution rates compared to other VO NPs. We orally dosed the five types of VO NPs (70 and 210µg/mouse, approximately 2 and 6mg/kg) to mice for 28 days and compared their biodistribution and toxic effects. We found that S-V2O5 and S-V2O3 NPs more accumulated in tissues compared to other three types of VO NPs, and the accumulated level was in order of heart>liver>kidney>spleen. Additionally, tissue levels of redox reaction-related elements and electrolytes (Na(+), K(+), and Ca(2+)) were most clearly altered in the heart of treated mice. Notably, all S- and C-VO NPs decreased the number of WBCs at the higher dose, while total protein and albumin levels were reduced at the higher dose of S-V2O5 and S-V2O3 NPs. Taken together, we conclude that the biodistribution and toxic effects of VO NPs depend on their dissolution rates and size (surface area). Additionally, we suggest that further studies are needed to clarify effects of VO NPs on functions of the heart and the immune system.

Influence of Primary Ligands (ODA, TDA) on Physicochemical and Biological Properties of Oxidovanadium (IV) Complexes with Bipy and Phen as Auxiliary Ligands.

The influence of the oxydiacetate (ODA) and thiodiacetate (TDA) ligands on the physicochemical and biological properties of the oxidovanadium(IV) ternary complexes of the VO(L)(B) type, where L denotes ODA or TDA and B denotes 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen), has been investigated. The stability of the complexes in aqueous solutions, assessed based on the potentiometric titration method, increases in the following direction: VO(TDA)(bipy) < VO(ODA)(bipy) < VO(TDA)(phen) < VO(ODA)(phen). Furthermore, the influence of the TDA and ODA ligands on the antioxidant activity of the oxidovanadium(IV) complexes toward superoxide free radical (O2•-), 2,2'-azinobis(3-ethylbenzothiazoline-6 sulfonic acid) cation radical (ABTS+•) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH•) has been examined and discussed. The reactivity of the complexes toward O2•- increases in the following direction: VO(TDA)(phen) < VO(TDA)(bipy) ≈ VO(ODA)(bipy) < VO(ODA)(phen). The antioxidant activity against ABTS+• and DPPH• free radicals is higher for phen complexes, whereas the thiodiacetate complexes are more reactive than are the corresponding oxydiacetate ones. Finally, herein, the cytoprotective activity of the complexes against the oxidative damage generated exogenously by hydrogen peroxide in the hippocampal neuronal HT22 cell line (the MTT and LDH tests) is reported. In a low concentration (1 µM), the cytoprotective action of thiodiacetate complexes is much higher than that of the corresponding oxydiacetate complexes. However, in the higher concentration range (10 and 100 µM), the antioxidant activity of the complexes is overcompensated by their cytotoxic effect.

Determination of mercury and vanadium concentration in Johnius belangerii (C) fish in Musa estuary in Persian Gulf.

The main aim of this study was to determine the concentrations of mercury and vanadium in Johnius belangerii (C) fish in the Musa estuary. A total of 67 fishes were caught from the Musa estuary during five intervals of 15days in the summer of 2013. After biometric measurements were conducted, the concentrations of mercury and vanadium were measured in the muscle tissue of fish using a direct method analyzer (DMA) and a graphite furnace atomic absorption spectrophotometer, respectively. The mean concentration of mercury and vanadium in the muscle tissue of fish was 3.154±1.981 and 2.921±0.873mg/kg w.w, respectively. The generalized linear model (GLM) analysis showed a significantly positive relationship among mercury concentration, length, and weight (P=0.000). In addition, there was a significantly negative relationship between vanadium concentration and fish length (P=0.000). A reverse association was found between concentrations of mercury and vanadium. Mercury concentration exceeded the allowable standards of the Environmental Protection Agency (EPA), the World Health Organization (WHO), and the Food and Drug Administration (FDA) in J. belangerii (C).

Effects of vanadium (V) and magnesium (Mg) on rat bone tissue: mineral status and micromorphology. Consequences of V-Mg interactions.

The extent to which the 12 week separate and combined administration of vanadium (as sodium metavanadate--SMV, 0.125 mg V per ml) and magnesium (as magnesium sulphate--MS, 0.06 mg Mg per ml) affects bone mineral status and micromorphology as well as the alkaline phosphatase (ALP) activity in femoral diaphysis (FD) was examined in male rats. The bone chemical composition of SMV-exposed rats was also investigated. SMV alone or in combination with MS (as SMV-MS) reduced the levels of MgFD (by 21% and 20%) and PFD (by 12% and 9%), lowered the CaFD content (by 7% and 10%), and caused a rise of the FeFD concentration (by 22.5% and 17%), compared with the control; SMV alone also reduced and enhanced the KFD and ZnFD concentrations (by 19% and 15%, respectively) but remained without significant effect on the femoral bone surface roughness (FBSR), whereas MS alone lowered the VFD, PFD, and CuFD levels (by 42%, 10%, and 20.6%), reduced FBSR, and created the regular femoral bone surface shape. The SMV-MS combination also induced a decline and rise in the levels of CuFD (by 30%) and NaFD (by 15%), respectively, compared with the control and the MS-supplemented rats; elevated ALPFD activity (by 24%, 35%, and 40%), compared with the control, SMV-exposed, and MS-supplemented animals; and increased FBSR. Relationships between the root mean square roughness (Sq) and skewness (Ssk): Sq [MS < SMV < Control < SMV-MS] ⇔ Ssk [SMV-MS > Control > SMV > MS], ALPFD and Sq: ALPFD⇔ Sq [SMV-MS > Control > SMV > MS], and between other variables were demonstrated. A partial limitation of the drop in the PFD and KFD levels and normalization of the ZnFD concentration were a consequence of the V-Mg antagonistic interaction whereas a consequence of the V-Mg synergistic interaction was the increase in the NaFD level, ALPFD activity, and FBSR. Ca10(PO4)5(SiO4)(OH) was part of the inorganic component of the bone of the SMV-exposed rats.

Essentiality and toxicity of vanadium supplements in health and pathology.

The biological properties of vanadium complexes have become an object of interest due to their therapeutic potential in several diseases. However, the mechanisms of action of vanadium salts are still poorly understood. Vanadium complexes are cofactors for several enzymes and also exhibit insulin-mimetic properties. Thus, they are involved in the regulation of glucose metabolism, including in patients with diabetes. In addition, vanadium salts may also normalize blood pressure and play a key role in the metabolism of the thyroid and of iron as well as in the regulation of total cholesterol, cholesterol HDL and triglyceride (TG) levels in blood. Moreover, in cases of hypoxia, vanadium compounds may improve cardiomyocytes function. They may also exhibit both carcinogenic and anti-cancer properties. These include dose- and exposure-time-dependent induction and inhibition of the proliferation and survival of cancer cells. On the other hand, the balance between vanadium's therapeutic properties and its side effects has not yet been determined. Therefore, any studies on the potential use of vanadium compounds as supplements to support the treatment of a number of diseases must be strictly monitored for adverse effects.

Correlation of insulin-enhancing properties of vanadium-dipicolinate complexes in model membrane systems: phospholipid langmuir monolayers and AOT reverse micelles.

We explore the interactions of V(III) -, V(IV) -, and V(V) -2,6-pyridinedicarboxylic acid (dipic) complexes with model membrane systems and whether these interactions correlate with the blood-glucose-lowering effects of these compounds on STZ-induced diabetic rats. Two model systems, dipalmitoylphosphatidylcholine (DPPC) Langmuir monolayers and AOT (sodium bis(2-ethylhexyl)sulfosuccinate) reverse micelles present controlled environments for the systematic study of these vanadium complexes interacting with self-assembled lipids. Results from the Langmuir monolayer studies show that vanadium complexes in all three oxidation states interact with the DPPC monolayer; the V(III) -phospholipid interactions result in a slight decrease in DPPC molecular area, whereas V(IV) and V(V) -phospholipid interactions appear to increase the DPPC molecular area, an observation consistent with penetration into the interface of this complex. Investigations also examined the interactions of V(III) - and V(IV) -dipic complexes with polar interfaces in AOT reverse micelles. Electron paramagnetic resonance spectroscopic studies of V(IV) complexes in reverse micelles indicate that the neutral and smaller 1:1 V(IV) -dipic complex penetrates the interface, whereas the larger 1:2 V(IV) complex does not. UV/Vis spectroscopy studies of the anionic V(III) -dipic complex show only minor interactions. These results are in contrast to behavior of the V(V) -dipic complex, [VO2 (dipic)](-) , which penetrates the AOT/isooctane reverse micellar interface. These model membrane studies indicate that V(III) -, V(IV) -, and V(V) -dipic complexes interact with and penetrate the lipid interfaces differently, an effect that agrees with the compounds' efficacy at lowering elevated blood glucose levels in diabetic rats.

Assessing human exposure to aluminium, chromium and vanadium through outdoor dust ingestion in the Bassin Minier de Provence, France.

The Western part of the "Bassin Minier de Provence", a former coal mining area, is still occupied by old polluting industries such as a coal-fired power plant and an alumina factory. The identified pollution sources that raise more concern in the population are the emission of gases and dusts, as well as the storage of raw and transformed materials. In 2011, a preliminary survey was carried out in the area as the first step to an exposure and health risk-assessment study. This first survey intends to assess human exposure through ingestion and health risk associated with potentially harmful elements (PHEs) in ground-level dusts collected in recreational areas used by children. Dust samples were taken at 19 sites distributed across the study area, depending on the location of public parks, public gardens, playgrounds and schools. Pseudo-total concentrations of 53 elements were determined by ICP-MS. Bioaccessible concentrations were estimated using the unified bioaccessibility method. This study presents the results obtained for Al, V and Cr, which seem to be related with industry and show similar distribution patterns. PHEs presumably related to traffic or other urban pollution sources are not discussed in this study. The highest total concentrations occur in dusts near the alumina plant that have significant amounts of Al mineral phases (gibbsite and alumina). However, in these dusts only small fractions of the elements under study are in bioaccessible forms. The highest bioaccessible fractions occur in dusts collected near the coal-fired power plant. Further investigation is required to assess potential pathways of exposure and health risk in this area.

Uptake and speciation of vanadium in the benthic invertebrate Hyalella azteca.

Vanadium has the potential to leach into the environment from petroleum coke, an oil sands byproduct. To determine uptake of vanadium species in the biota, we exposed the benthic invertebrate Hyalella azteca with increasing concentrations of two different vanadium species, V(IV) and V(V), for seven days. The concentrations of vanadium in the H. azteca tissue increased with the concentration of vanadium in the exposure water. Speciation analysis revealed that V(IV) in the exposure water was oxidized to V(V) between renewal periods, and therefore the animals were mostly exposed to V(V). Speciation analysis of the H. azteca tissue showed the presence of V(V), V(IV), and an unidentified vanadium species. These results indicate the uptake and metabolism of vanadium by H. azteca. Because H. azteca are widely distributed in freshwater systems and are an important food supply for many fish, determining the uptake and metabolism of vanadium allows for a better understanding of the potential environmental effects on invertebrates.

The use of feathers in monitoring bioaccumulation of metals and metalloids in the South African endangered African grass-owl (Tyto capensis).

Few studies have quantified metals in South African species and no published data on residues specifically in South African owl feathers exist. Tyto capensis is listed as vulnerable within South Africa, making it preferable to use a non-invasive technique to determine metal bioaccumulation for this species. Comparisons are made with the cosmopolitan T. alba to determine whether this species could be used as a surrogate. Concentrations of various metals were thus determined in feathers of the two species and compared with liver and muscle samples. Samples were taken from 119 owls collected as road kill along a national road. A comparison of concentrations in feathers revealed similarly higher concentrations of aluminium, antimony, lead, nickel, and strontium, whereas concentrations of chromium, copper, iron, manganese, selenium, titanium and zinc were similarly higher in internal tissues for both species. Metal concentrations of owls were comparable to those reported in literature and below toxic levels, suggesting that these metals were not likely to impact the owls. Further regressions between feathers and corresponding livers were examined to determine if feathers were indicative of internal metal burdens. Significant positive relationships were found for aluminium, copper, lead, nickel and vanadium in T. alba and nickel, manganese and vanadium in T. capensis. Preliminary results support the feasibility of using feathers as non-destructive indicators of environmental contamination in T. capensis although caution needs to be taken when interpreting the results.

Correlation analysis as a tool to investigate the bioaccessibility of nickel, vanadium and zinc in Northern Ireland soils.

Correlation analyses were conducted on nickel (Ni), vanadium (V) and zinc (Zn) oral bioaccessible fractions (BAFs) and selected geochemistry parameters to identify specific controls exerted over trace element bioaccessibility. BAFs were determined by previous research using the unified BARGE method. Total trace element concentrations and soil geochemical parameters were analysed as part of the Geological Survey of Northern Ireland Tellus Project. Correlation analysis included Ni, V and Zn BAFs against their total concentrations, pH, estimated soil organic carbon (SOC) and a further eight element oxides. BAF data were divided into three separate generic bedrock classifications of basalt, lithic arenite and mudstone prior to analysis, resulting in an increase in average correlation coefficients between BAFs and geochemical parameters. Sulphur trioxide and SOC, spatially correlated with upland peat soils, exhibited significant positive correlations with all BAFs in gastric and gastro-intestinal digestion phases, with such effects being strongest in the lithic arenite bedrock group. Significant negative relationships with bioaccessible Ni, V and Zn and their associated total concentrations were observed for the basalt group. Major element oxides were associated with reduced oral trace element bioaccessibility, with Al2O3 resulting in the highest number of significant negative correlations followed by Fe2O3. spatial mapping showed that metal oxides were present at reduced levels in peat soils. The findings illustrate how specific geology and soil geochemistry exert controls over trace element bioaccessibility, with soil chemical factors having a stronger influence on BAF results than relative geogenic abundance. In general, higher Ni, V and Zn bioaccessibility is expected in peat soil types.

Differential gene regulation by V(IV) and V (V) ions in the branchial sac, intestine, and blood cells of a vanadium-rich ascidian, Ciona intestinalis.

Ascidians are hyperaccumulators that have been studied in detail. Proteins and genes involved in the accumulation process have been identified, but regulation of gene expression related to vanadium accumulation remains unknown. To gain insights into the regulation of gene expression by vanadium in a genome-wide manner, we performed a comprehensive study on the effect of excess vanadium ions on a vanadium-rich ascidian, Ciona intestinalis, using a microarray. RT-PCR and enzyme activity assay were performed from the perspective of redox and accumulation of metal ions in each tissue. Glutathione metabolism-related proteins were significantly up-regulated by V(IV) treatment. Several genes involved in the transport of vanadium and protons, such as Nramp and V-ATPase, were significantly up-regulated by V(IV) treatment. We observed significant up-regulation of glutathione synthesis and degradation pathways in the intestine and branchial sac. In blood cells, expression of Ci-Vanabin4, glutathione reductase activity, glutathione levels, and vanadium concentration increased after V(IV) treatment. V(IV) treatment induced significant changes related to vanadium exclusion, seclusion, and redox pathways in the intestine and branchial sac. It also induced an enhancement of the vanadium reduction and accumulation cascade in blood cells. These differential responses in each tissue in the presence of excess vanadium ions suggest that vanadium accumulation and reduction may have regulatory functions. This is the first report on the gene regulation by the treatment of vanadium-rich ascidians with excess vanadium ions. It provided much information for the mechanism of regulation of gene expression related to vanadium accumulation.

Vanadium accumulation in ascidian coelomic cells is associated with enhanced pentose phosphate pathway capacity but not overall aerobic or anaerobic metabolism.

Some suborders of ascidians (sea squirts) accumulate remarkable levels of the heavy metal vanadium while others accumulate negligible amounts. The function of this vanadium is unclear, but enhanced pentose phosphate pathway (PPP) has been implicated in its reduction and accumulation. We compared aspects of intermediary metabolism in coelomic cells from ascidian species that have a wide range of vanadium accumulation including non-accumulators. All species appear to have similar aerobic poise with no apparent link to vanadium accumulation. Similarly, all species examined have a limited anaerobic poise that does not seem to relate to vanadium levels. Based on the activities of phosphoglucose isomerase and glucose-6 phosphate dehydrogenase we demonstrate that, relative to the capacity for entry into glycolysis, vanadium-accumulating species have enhanced capacity to metabolize glucose-6 phosphate via the PPP compared to non-accumulators. This finding provides the first comparative support for enhanced PPP capacity linked to vanadium accumulation in tunicates.