Potential health impacts from different vegetable nitrate intake scenarios and providing strategies to manage the risks for Iranian population.

Health risk from nitrate was predicted for different scenarios of vegetable consumption and nitrate contents in Iran. Finally, certain management scenarios were presented for nitrate risk mitigation under worst-case scenario considering each vegetable contribution in nitrate intake. Two fruit (bell pepper and tomato) and two leafy vegetables (lettuce and mint) were sampled in a combined randomized method from fields, greenhouses, and markets of Isfahan province, Iran during October to December 2015. To assess the potential health impacts of nitrate from the vegetable ingestion, the present status and three different scenarios of increasing vegetable consumption and/or increasing plant nitrate concentrations were considered. Two management scenarios for reducing the total nitrate intake below the allowable values were predicted. By increasing vegetable consumption under scenario 1 and nitrate concentration under scenario 3, the total hazard quotient (THQs) was increased, although the highest increase (12-fold) in the THQs was provided by lettuce. Health risk from nitrate for sensitive groups was effectively reduced by a 70% decrease in lettuce nitrate concentration. In the second management scenario, decreasing upper nitrate concentrations in the other sources (except lettuce) by 30% declined nitrate intake in children (< 6 years old) and boys (7-14 years old) below acceptable daily intake (ADI). By taking into account the increases in the amounts of consumption and nitrate in vegetables at different scenarios, it was revealed that the critical factor for a high dietary exposure to nitrate is not the absolute amount of vegetables consumed but the type of vegetable (lettuce) and the concentration of nitrate related to the conditions of production. Therefore, to manage any risks to human health from dietary nitrate exposure resulting from vegetable consumption, focus on lettuce instead of taking other vegetables equally into account is needed.

Effect of low molecular weight organic acids on the uptake of 226Ra by corn (Zea mays L.) in a region of high natural radioactivity in Ramsar-Iran.

To study the benefit of including citric and oxalic acid treatments for phytoremediation of 226Ra contaminated soils a greenhouse experiment with corn was conducted. A soil was sampled from a region of high natural 226Ra radioactivity in Ramsar, Iran. After cultivation of corn seed and using organic acid treatments at 1, 10 and 100 mM concentrations, plants (shoots and roots) were harvested, digested and prepared to measure 226Ra activity. Simultaneously, sequential selective extraction were performed to estimate the partitioning of 226Ra among geochemical extraction. Results showed that the maximum uptake of 226Ra in plants was observed in citric acid (6.3%) and then oxalic acid (6%) at 100 mM concentration. These treatments increased radium uptake by a factor of 1.5 than the control. Enhancement of radium uptake by plants was related to soil pH reduction of organic acids in comparison to control. Also, the maximum uptake of this radionuclide in all treatments was obtained in roots compared to shoots. 226Ra fractionations results revealed that 91.8% of radium was in the residual phase of the soil and the available fractions were less than 2%. As the main percent of 226Ra was in the residual phase of the soil in this region, it seems that organic acids had not significant effect on the uptake of 226Ra for phytoremediation by corn in this condition.

The interaction of boron with goethite: experiments and CD-MUSIC modeling.

Boron (B) is an essential element for plants and animals growth that interacts with mineral surfaces regulating its bioavailability and mobility in soils, sediments, and natural ecosystems. The interaction with mineral surfaces is quite important because of a narrow range between boron deficiency and toxicity limits. In this study, the interaction of boric acid with goethite (α-FeOOH) was measured in NaNO(3) background solution as a function of pH, ionic strength, goethite and boron concentration representing as adsorption edges and isotherms. Boron adsorption edges showed a bell-shaped pattern with maximum adsorption around pH 8.50, whereas adsorption isotherms were rather linear. The adsorption data were successfully described with the CD-MUSIC model in combination with the Extended Stern (ES) model. The charge distribution (CD) of inner-sphere boron surface complexes was calculated from the geometry optimized with molecular orbital calculations applying density functional theory (MO/DFT). The CD modeling suggested dominant binding of boric acid as a trigonal inner-sphere complex with minor contributions of a tetrahedral inner-sphere complex (at high pH) and a trigonal outer-sphere complex (at low pH). The interpretation with the CD model is consistent with the spectroscopic observations.

Diffusion of neutral and ionic species in charged membranes: boric acid, arsenite, and water.

Dynamic ion speciation using DMT (Donnan membrane technique) requires insight into the physicochemical characteristics of diffusion in charged membranes (tortuosity, local diffusion coefficients) as well as ion accumulation. The latter can be precluded by studying the diffusion of neutral species, such as boric acid, B(OH)3°(aq), arsenite, As(OH)3°(aq), or water. In this study, the diffusion rate of B(OH)3° has been evaluated as a function of the concentration, pH, and ionic strength. The rate is linearly dependent on the concentration of solely the neutral species, without a significant contribution of negatively charged species such as B(OH)4⁻, present at high pH. A striking finding is the very strong effect (factor of ~10) of the type of cation (K(+), Na(+), Ca(2+), Mg(2+), Al(3+), and H(+)) on the diffusion coefficient of B(OH)3° and also As(OH)3°. The decrease of the diffusion coefficient can be rationalized as an enhancement of the mean viscosity of the confined solution in the membrane. The diffusion coefficients can be described by a semiempirical relationship, linking the mean viscosity of the confined solute of the membrane to the viscosity of the free solution. In proton-saturated membranes, as used in fuel cells, viscosity is relatively more enhanced; i.e., a stronger water network is formed. Extraordinarily, our B(OH)3-calibrated model (in HNO3) correctly predicts the reported diffusion coefficient of water (D(H2O)), measured with ¹H NMR and quasi-elastic neutron scattering in H(+)-Nafion membranes. Upon drying these membranes, the local hydronium, H(H2O)(n)(+), concentration and corresponding viscosity increase, resulting in a severe reduction of the diffusion coefficient (D(H2O) ≈ 5-50 times), in agreement with the model. The present study has a second goal, i.e., development of the methodology for measuring the free concentration of neutral species in solution. Our data suggest that the free concentration can be measured with DMT in natural systems if one accounts for the variation in the cation composition of the membrane and corresponding viscosity/diffusion coefficient.

Adsorption and desorption processes of boron in calcareous soils.

Boron (B) availability is regulated by its equilibrium concentration that in turn is buffered by adsorption and desorption reactions. Ionic strength, pH, OM content, and the type and amount of minerals are the major factors affecting B sorption reactions. To evaluate the influence of calcium carbonate equivalent (CCE) and ionic strength on B chemical behavior, its adsorption and desorption isotherms were measured in eight calcareous soils differed in CCE (0-85%). Adsorption and desorption data were described by the Langmuir and the Linear adsorption equations, respectively. No statistically significant relation was found between model parameters and soil properties. However, in comparison, soils with higher reactive particles (clay and OM) and higher pH adsorbed more boron. Removing CCE from a soil sample (CCE=18%) lowered B adsorption maximum by 35%. In contrast, increasing electrolyte concentration (0.01 M NaCl) to 0.1 and 0.5M caused to increase B adsorption maximum by 30% and 75%, respectively. At the equi-molar concentration, CaCl(2) increased B adsorption stronger than NaCl. The positive effect of ionic strength was attributed to a better screening of surface charges and compaction of double layer thickness. Desorption data were deviated from adsorption isotherms only at equilibrium concentrations smaller than 2 mM. Analysis of boron solution speciation and adsorption-desorption data revealed that B is mainly adsorbed as spectroscopically proved outer-sphere complex in the studied soil samples. The experimental data and model prediction could be used to manage B bio-availability and to optimize remediation processes in calcareous soils.