Spectral Detection of Nanophase Iron Minerals Produced by Fe(III)-Reducing Hyperthermophilic Crenarchaea.

Mineral transformations by two hyperthermophilic Fe(III)-reducing crenarchaea, Pyrodictium delaneyi and Pyrobaculum islandicum, were examined using synthetic nanophase ferrihydrite, lepidocrocite, and akaganeite separately as terminal electron acceptors and compared with abiotic mineral transformations under similar conditions. Spectral analyses using visible-near-infrared, Fourier-transform infrared attenuated total reflectance (FTIR-ATR), Raman, and Mössbauer spectroscopies were complementary and revealed formation of various biomineral assemblages distinguishable from abiotic phases. The most extensive biogenic mineral transformation occurred with ferrihydrite, which formed primarily magnetite with spectral features similar to biomagnetite relative to a synthetic magnetite standard. The FTIR-ATR spectra of ferrihydrite bioreduced by P. delaneyi also showed possible cell-associated organics such as exopolysaccharides. Such combined detections of biomineral assemblages and organics might serve as biomarkers for hyperthermophilic Fe(III) reduction. With lepidocrocite, P. delaneyi produced primarily a ferrous carbonate phase reminiscent of siderite, and with akaganeite, magnetite and a ferrous phosphate phase similar to vivianite were formed. P. islandicum showed minor biogenic production of a ferrous phosphate similar to vivianite when grown on lepidocrocite, and a mixed valent phosphate or sulfate mineral when grown on akaganeite. These results expand the range of biogenic mineral transformations at high temperatures and identify spacecraft-relevant spectroscopies suitable for discriminating mineral biogenicity.

Effect of ferric chloride on phosphorus immobilization and speciation in Dianchi Lake sediments.

Immobilization of phosphorus in lake sediments and control of internal-loading phosphorus release have become crucial aspects of eutrophication lake management. In this study, the immobilization efficiency of phosphorus by ferric chloride in Dianchi Lake sediments was investigated. In addition, effects of the dosage of ferric chloride and contact time on the release of phosphorus from sediments were investigated. Laboratory experiments revealed that ferric chloride can effectively inhibit the release of phosphorus from sediments. At a ferric chloride dosage of 10 mg/g, the total phosphorus concentration of the overlying water was reduced by ~87%. With the increase in the contact time, the amount of phosphorus immobilized by ferric chloride increased. To further evaluate the feasibility of ferric chloride for immobilising phosphorus in sediments, an amplification experiment with a water volume of 50 L was carried out. By the addition of 6 mg/g of ferric chloride, the total phosphorus concentration of the overlying water was still less than 0.01 mg/L after 100 days. At the same time, the phosphorus species in the sediment after treatment with ferric chloride were analyzed. Results revealed that ferric chloride mainly converts unstable exchangeable phosphorus (Ex-P), ferric phosphate (Fe-P) and organic phosphorus (Or-P) into more stable occluded phosphate (O-P), reducing the possible release of phosphorus from sediments. Practical applications of ferric chloride to control the release of phosphorus from Dianchi Lake sediments were discussed.

Using magnetic particle imaging systems to localize and guide magnetic hyperthermia treatment: tracers, hardware, and future medical applications.

Magnetic fluid hyperthermia (MFH) treatment makes use of a suspension of superparamagnetic iron oxide nanoparticles, administered systemically or locally, in combination with an externally applied alternating magnetic field, to ablate target tissue by generating heat through a process called induction. The heat generated above the mammalian euthermic temperature of 37°C induces apoptotic cell death and/or enhances the susceptibility of the target tissue to other therapies such as radiation and chemotherapy. While most hyperthermia techniques currently in development are targeted towards cancer treatment, hyperthermia is also used to treat restenosis, to remove plaques, to ablate nerves and to alleviate pain by increasing regional blood flow. While RF hyperthermia can be directed invasively towards the site of treatment, non-invasive localization of heat through induction is challenging. In this review, we discuss recent progress in the field of RF magnetic fluid hyperthermia and introduce a new diagnostic imaging modality called magnetic particle imaging that allows for a focused theranostic approach encompassing treatment planning, treatment monitoring and spatially localized inductive heating.

Validation of MRI quantitative susceptibility mapping of superparamagnetic iron oxide nanoparticles for hyperthermia applications in live subjects.

The use of magnetic fluid hyperthermia (MFH) for cancer therapy has shown promise but lacks suitable methods for quantifying exogenous irons such as superparamagnetic iron oxide (SPIO) nanoparticles as a source of heat generation under an alternating magnetic field (AMF). Application of quantitative susceptibility mapping (QSM) technique to prediction of SPIO in preclinical models has been challenging due to a large variation of susceptibility values, chemical shift from tissue fat, and noisier data arising from the higher resolution required to visualize the anatomy of small animals. In this study, we developed a robust QSM for the SPIO ferumoxytol in live mice to examine its potential application in MFH for cancer therapy. We demonstrated that QSM was able to simultaneously detect high level ferumoxytol accumulation in the liver and low level localization near the periphery of tumors. Detection of ferumoxytol distribution in the body by QSM, however, required imaging prior to and post ferumoxytol injection to discriminate exogenous iron susceptibility from other endogenous sources. Intratumoral injection of ferumoxytol combined with AMF produced a ferumoxytol-dose dependent tumor killing. Histology of tumor sections corroborated QSM visualization of ferumoxytol distribution near the tumor periphery, and confirmed the spatial correlation of cell death with ferumoxytol distribution. Due to the dissipation of SPIOs from the injection site, quantitative mapping of SPIO distribution will aid in estimating a change in temperature in tissues, thereby maximizing MFH effects on tumors and minimizing side-effects by avoiding unwanted tissue heating.

Fluorometric assay of iron(II) lactate hydrate and ammonium ferric citrate in food and medicine based on poly(sodium-p-styrenesulfonate)-enhanced Ag nanoclusters.

Poly(sodium-p-styrenesulfonate)-enhanced and D-penicillamine stabilized Ag nanoclusters (PSS-DPA-AgNCs) were prepared using one-step ultraviolet irradiation combined with microwave heating method, and the effects of the AgNCs photo-luminescence performance based on different types of polyelectrolytes and energy suppliers were studied detailedly. The as-prepared AgNCs can be used as a viable fluorescent probe for monitoring indirectly iron(II) lactate hydrate (ILH) and ammonium ferric citrate (AFC), respectively. The fluorescence (FL) quenching of PSS-DPA-AgNCs by Fe3+ (it is obtained from oxidized ILH/ionized AFC) mainly derives from a dynamic quenching process. Excellent linear relationships exist between the FL quenching degree of the AgNCs and the concentrations of ILH/AFC in the range of 0.17-6.00/0.067-3.33 µmol·L-1, and corresponding limit of detection (at 3σ/slope) is 12.4/6.04 nmol·L-1. Moreover, the AgNCs probe was extended to the assays of ILH in tablets, solid beverage or ILH additive and AFC in two kinds of edible salts or syrup with satisfactory results compared with the standard 1, 10-phenanthroline method. In addition, the AgNCs probe reveals a good temperature sensing capability.

Chemometric Analysis of Antioxidant and Mineral Elements in Colostrum of Native and Non-native Goat Breeds to Hypoxic Conditions at High Altitude.

Colostrum of goat is a well-known nutritional source of animal product, which is attributed to innumerable nutritional properties. To enrich nutritional resources for understanding various nutritional values of animal product at high altitude, chemometric analysis of antioxidant and mineral element study was carried out by comparing antioxidants capacity, free radical scavenging activity, and certain mineral elements in colostrums of native and non-native goat breeds. Colostrum samples were collected from native Changthangi (CNG) and non-native Sirohi (SIRO) goat breeds, situated at naturally exposed high altitude of 3505.2 m above mean sea level. The antioxidant of samples was measured by ferric reducing ability of plasma (FRAP) and 2, 2-diphenyl-1-picrylhydrazyl (DPPH) activity assay, and mineral elemental quantification of Fe, Mg, Mn, Zn, Co, Cu, K, Ca, B, Ni, and Cr was performed using ICP-OES. The values of FRAP, DPPH, and Fe, Mg, Mn, Zn, Co, Cu, K, and Ca in colostrums of native goat breed was significantly (p ≤ 0.05) higher than the non-native goat. These data conclude that high altitude native goat has more antioxidant and mineral elements in colostrum than non-native colostrum. This study could provide a basis for establishing the role of colostrum supplements as a natural source to strengthen the endurance to modalities for the survival of newborn kids of goat within the native high altitude environment. This is the first report of a comparative chemometric analysis of colostrums of goat species and can be utilized to characterize the nutritional aspect of animal product with unique antioxidant and mineral nutrients composition in colostrum of goat.

The Application of Ferric Chloride-Lignin Sulfonate as Shale Inhibitor in Water-Based Drilling Fluid.

A series of ferric chloride-lignin sulfonate (FCLS) was prepared from ferric chloride and lignin sulfonate to be used as shale inhibitor. The swelling rate of clay with FCLS-2 (w/w = 0.3%) decreased to 41.9%. Compared with control, FCLS-2 displayed high inhibitive ability against the hydrating and swelling processes of clay. Thus, the swelling degree of samples with FCLS-2 was much lower than that of the control, as well as the mud ball was more stable in FCLS-2 solution. Essentially, these excellent performances in inhibitor were assigned to the hydrogen bonding, electrostatic interaction and anchoring between FCLS-2 and other components. In addition, FCLS-2 has good compatibility with other common drilling fluid additives, and it can reduce the viscosity of systems, regardless of the room temperature or high temperature.

Metal/metalloid and phosphorus characteristics in porewater associated with manganese geochemistry: A case study in the Jiulong River Estuary, China.

Sediment porewater can be an important source of contaminants in the overlying water, but the mechanisms of metal(loid) and phosphorus (P) remobilization remain to be investigated. In this study, high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) samplers were used to determine the porewater dissolved iron (Fe), manganese (Mn), cobalt (Co), chromium (Cr), vanadium (V), selenium (Se), arsenic (As), P and DGT-Labile S in coastal sediments in the Jiulong River Estuary (JRE), China. The results showed that high concentrations of dissolved Mn, Se and P were present in the overlying water, indicating potential water pollution with excessive amounts of Mn, Se and P. The dissolved Mn concentrations in the porewater were higher than the dissolved Fe concentrations, especially at submerged sites, demonstrating that Mn(III/IV) reduction is the dominant diagenetic pathway for organic carbon (OC) degradation, which directly affects Fe cycling by the competitive inhibition of Fe(III) reduction and Fe(II) reoxidation. Dissolved Co, Cr, V, Se, As and P show significant positive correlations with Mn but nearly no correlations with Fe, suggesting that the mobility of these metal(loid)s and P is associated with Mn but not Fe cycling in this region. In addition, the coelevated concentrations of the metal(loid)s, P and Mn at the submerged sites are attributed to the strengthened Mn reduction coupled with OC degradation fueled by hypoxia. The higher positive diffusion fluxes of Mn, Se and P were consistent with the excess Mn, Se and P concentrations in the overlying water, together with the approximately positive fluxes of the other metal(loid)s, indicating that sediment Mn(III/IV) reduction and concomitant metal(loid) and P remobilization might be vital pathways for metal(loid) and P migration to the overlying water.

Optimization and Design of Magnetic Ferrite Nanoparticles with Uniform Tumor Distribution for Highly Sensitive MRI/MPI Performance and Improved Magnetic Hyperthermia Therapy.

Two major technical challenges of magnetic hyperthermia are quantitative assessment of agent distribution during and following administration and achieving uniform heating of the tumor at the desired temperature without damaging the surrounding tissues. In this study, we developed a multimodal MRI/MPI theranostic agent with active biological targeting for improved magnetic hyperthermia therapy (MHT). First, by systematically elucidating the magnetic nanoparticle magnetic characteristics and the magnetic resonance imaging (MRI) and magnetic particle imaging (MPI) signal enhancement effects, which are based on the magnetic anisotropy, size, and type of nanoparticles, we found that 18 nm iron oxide NPs (IOs) could be used as superior nanocrystallines for high performance of MRI/MPI contrast agents in vitro. To improve the delivery uniformity, we then targeted tumors with the 18 nm IOs using a tumor targeting peptide, CREKA. Both MRI and MPI signals showed that the targeting agent improves the intratumoral delivery uniformity of nanoparticles in a 4T1 orthotopic mouse breast cancer model. Lastly, the in vivo antitumor MHT effect was evaluated, and the data showed that the improved targeting and delivery uniformity enables more effective magnetic hyperthermia cancer ablation than otherwise identical, nontargeting IOs. This preclinical study of image-guided MHT using cancer-targeting IOs and a novel MPI system paves the way for new MHT strategies.

Differences in main processes to transform phosphorus influenced by ammonium nitrogen in flooded intensive agricultural and steppe soils.

Exogenous ammonium nitrogen (AN) fertilization/deposition and the subsequently induced soil acidification, might exacerbate soil phosphorus (P) transformation and mobility, whereas poor understanding in abiotic and biotic processes still existed between intensively cultivated soil with high proportion of legacy inorganic P (Pi) in comparison to natural steppe soil with high proportion of organic P (Po). Column batch flooded experiment using vegetable (VEG) and steppe (STE) soils was conducted to investigate the P transformation and mobility influenced by 60-day intermittent elution with an (1500 mg N kg-1) solution or an acid sulfate (107 mmol H+ kg-1) solution. The results showed that AN elution significantly decreased the contents of all Pi fractions and strengthened Pi leaching, whereas acid elution increased the contents of Al-Pi, Fe-Pi, and reductant-soluble Pi and reduced P leaching in VEG soil. In contrast, AN elution increased the contents of soluble-Po and Al-(Pi + Po) and decreased Ca-P and Fe-Pi, no effects on P leaching, whereas acid elution increased the contents of soluble-(Pi + Po), Al-(Pi + Po), Fe-(Pi + Po) and reduced P leaching in STE soil. Variances analysis showed that pH and microbial biomass carbon were the most important factors to predict the P composition of the VEG and the STE soil, respectively. This indicated that AN elution released the soil mineral-bound phosphate with ammonia oxidation coupled with Fe(III) reduction, besides the same chemical influences on Fe/Al oxides as acid elution in VEG soil; while predominantly affected biochemical/biological processes of soil P by changing microbial biomass and enzyme activities in STE soil.

Sediment potentially controls in-lake phosphorus cycling and harmful cyanobacteria in shallow, eutrophic Utah Lake.

Lakes worldwide are impacted by eutrophication and harmful algal or cyanobacteria blooms (HABs) due to excessive nutrients, including legacy P released from sediments in shallow lakes. Utah Lake (northern Utah, USA) is a shallow lake with urban development primarily on the east side of the watershed, providing an opportunity to evaluate HABs in relation to a gradient of legacy sediment P. In this study, we investigated sediment composition and P concentrations in sediment, pore water, and the water column in relation to blooms of harmful cyanobacteria species. Sediments on the east side of the lake had P concentrations up to 1710 mg/kg, corresponding to elevated P concentrations in pore water (up to 10.8 mg/L) and overlying water column (up to 1.7 mg/L). Sediment P concentrations were positively correlated with Fe2O3, CaO, and organic matter abundance, and inversely correlated with SiO2, demonstrating the importance of sediment composition for P sorption and mineral precipitation. Although the sediment contained <3% Fe2O3 by weight, approximately half of the sediment P was associated with redox-sensitive Fe oxide/hydroxide minerals that could be released to the water column under reducing conditions. Cyanobacteria cell counts indicate that blooms of Aphanizomenon flos-aquae and Dolichospermum flosaquae species tend to occur on the east side of Utah Lake, corresponding to areas with elevated P concentrations in the sediment, pore water, and water column. Our findings suggest that shallow lake eutrophication may be a function of P in legacy sediments that contribute to observed HABs in specific locations of shallow lakes.

Selenium and mercury in Brazilian Cerrado soils and their relationships with physical and chemical soil characteristics.

The objective of this study was to determine the natural concentrations of Hg and Se in 45 representative soil profiles from the Cerrado biome in central Brazil, and to correlate their concentrations with soil chemical and physical characteristics. The study area was composed of three sub-regions: Goiás, Northwest of Minas Gerais, and Minas Gerais Triangle. Selenium and Hg concentrations were determined by acid digestion and atomic absorption spectroscopy. Data were subjected to analysis of variance on the means of the Hg and Se variables within each soil class at two depths, followed by multivariate statistical methods. The Hg concentrations ranged from 15 to 182 µg kg-1 and the Se concentrations ranged from 22 to 72 µg kg-1. The soil characteristics that most contributed to Hg concentrations in the soils, according to principal component analysis, were Fe2O3, FeO, TiO2, pH, P2O5, and effective CEC. In general, the soils of the Cerrado biome have deficient Se concentrations. The Humic Rhodic Acrustoxes have Hg concentrations above the prevention reference value for soils of Minas Gerais.

Quantitative assessment of the metabolic products of iron oxide nanoparticles to be used as iron supplements in cell cultures.

Iron nanoparticles (NPs) metabolism is directly associated to human health due to their use as anemia treatment and should be studied in detail in cells. Here we present a speciation strategy for the determination of the metabolic products of iron oxide nanoparticles coated by tartaric and adipic acids in enterocytes-like cell models (Caco-2 and HT-29). Such methodology is based on the use of SDS-modified reversed phase high performance liquid chromatography (HPLC) separation using inductively coupled plasma-mass spectrometry (ICP-MS) as Fe selective detector. Post-column isotope dilution analysis is used as quantification tool by adding 57Fe as isotopically enriched standard. To assess the separation capability of the method, two different iron nanostructures: iron sucrose nanoparticles -Venofer®- used as model suspension and iron tartrate/adipate-modified nanoparticles, both of about 4 nm (core size) were evaluated. The two nanostructures were injected into the system showing good peak profiles and quantitative elution recoveries (>80%) in both cases. In addition, both nanoparticulate fractions could be based-line separated from ionic iron species, which needed to be complexed with 1 mM citrate to elute from the column. Exposed cells up to 0.5 mM of iron tartrate/adipate-modified nanoparticles were specifically treated to extract the internalized NPs and the extracts examined using the proposed strategy. The obtained results revealed the presence of three different fractions corresponding to nanoparticle aggregates, dispersed nanoparticles and soluble iron respectively in a single chromatographic run. Quantitative experiments (column recoveries ranging from 60 to 80%) revealed the presence of the majority of the Fe in the nanoparticulated form (>75%) by summing up the dispersed and aggregate particles. Such experiments point out the high uptake and low solubilization rate of the tartrate/adipate NPs making these structures highly suitable as Fe supplements in oral anemia treatments.

Reductive decolorization of azo dyes via in situ generation of green tea extract-iron chelate.

In this study, rapid decolorization of azo dyes was achieved by in situ-generated green tea extract-iron (GTE-Fe) chelate for the first time. When changing reaction conditions from the aerobic condition to the anaerobic condition, the decolorization efficiencies of two azo dyes, i.e., acid orange 7 (AO7) and acid black 1 (AB1), increased from 46.38 and 83.17 to 90.13 and 95.37%, respectively. The recalcitrant AO7 was then selected as the targeting pollutant in subsequent optimization and mechanism studies. Experimental evidences showed that the initial concentrations of AO7, Fe(III), and GTE are the key factors to optimize the decolorization efficiency. Further characterization studies by spectroscopic analysis, including FESEM, FTIR, and XPS, suggested that the major mechanism of AO7 decolorization is the nucleophilic attack of the oxygen in green tea polyphenols (GTP), and this attack could be facilitated by the organometal chelation. This study provided an efficient and environmental friendly strategy to decolorize azo dyes via in situ generation of the GTE-Fe chelate, as well as its mechanistic insights, shedding lights on in situ remediation of azo dye pollution. Graphical abstract ᅟ.

Waste chimney oil to nanolights: A low cost chemosensor for tracer metal detection in practical field and its polymer composite for multidimensional activity.

Proper waste disposal from household and restaurants is becoming an important and recurring waste-management concern. Herein, a method of upcycling of waste kitchen chimney oil has been adopted to prepare fluorescent multifunctional carbon quantum dots. These nanodots showed superior biocompatibility, excellent optical properties, water solubility and high yield. Preparation of C-dots from highly abundant carbon source of waste refusals is highly effective in commercial aspect as well as in reducing the immense environmental pollution. The C-dots showed quasi-spherical size obtained from high resolution transmission electron microscopy (HRTEM) having an abundance of 1-4 nm in size. The ease of water dispersibility of the nanodots is a mere reflection of their surface polarity which has been supported by Fourier transformed infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). In the field of practical acceptability, the C-dots have been experimented to sense Fe3+ ion in a wide range of concentration (1 nM to 600 µM) with a detection limit of 0.18 nM which can be termed as 'tracer metal chemosensor'. Moreover, the prepared carbon dots were also tested against inter-cellular Fe3+ ion sensing probe. Lastly, we also fabricate the biopolymer­carbon dots composite for fluorescent marker ink and light emitting polymer film.

Dynamic probabilistic material flow analysis of nano-SiO2, nano iron oxides, nano-CeO2, nano-Al2O3, and quantum dots in seven European regions.

Static environmental exposure assessment models based on material flow analysis (MFA) have previously been used to estimate flows of engineered nanomaterials (ENMs) to the environment. However, such models do not account for changes in the system behavior over time. Dynamic MFA used in this study includes the time-dependent development of the modelling system by considering accumulation of ENMs in stocks and the environment, and the dynamic release of ENMs from nano-products. In addition, this study also included regional variations in population, waste management systems, and environmental compartments, which subsequently influence the environmental release and concentrations of ENMs. We have estimated the flows and release concentrations of nano-SiO2, nano-iron oxides, nano-CeO2, nano-Al2O3, and quantum dots in the EU and six geographical sub-regions in Europe (Central Europe, Northern Europe, Southern Europe, Eastern Europe, South-eastern Europe, and Switzerland). The model predicts that a large amount of ENMs are accumulated in stocks (not considering further transformation). For example, in the EU 2040 Mt of nano-SiO2 are stored in the in-use stock, 80,400 tonnes have been accumulated in sediments and 65,600 tonnes in natural and urban soil from 1990 to 2014. The magnitude of flows in waste management processes in different regions varies because of differences in waste handling. For example, concentrations in landfilled waste are lowest in South-eastern Europe due to dilution by the high amount of landfilled waste in the region. The flows predicted in this work can serve as improved input data for mechanistic environmental fate models and risk assessment studies compared to previous estimates using static models.

Enhanced iron(III) reduction following amendment of paddy soils with biochar and glucose modified biochar.

Although biochar application to paddy fields has been widely studied, its effects on Fe(III) reduction have not yet been investigated. Paddy soil slurry and soil microbial inoculation incubation were conducted with unmodified biochar (UMB) or glucose-modified biochar (GMB) additions at different particle sizes. The Fe(II) concentration and pH value were determined regularly, and Fe(III) reducing capacity (FeRC) was evaluated by modeling. Fe(III) reduction potential (a) was increased by 0-1.96 mg g-1 in response to UMBs addition, and a more remarkable increase in a was related to the decrease of particle size. The dissolved organic carbon of UMBs was responsible for the majority of the biochar reducing capacity. UMBs addition increased the contribution of free Fe and nitrate nitrogen to FeRC, while it decreased that of available phosphorus. Moreover, GMBs led to greater promotion of FeRC than the corresponding UMBs, with an increase in a of 2.9-16% in soil slurry and reduction rate of 13-35% in microbial inoculation incubation. The maximum Fe(III) reduction rate (V max) with GMBs addition was faster or invariable than UMBs, while the time to V max (T Vmax) was shorter or stable. The effect of GMBs on Fe(III) reduction was less sensitive as GMB particle size increased. Compared with UMBs addition, pH declined remarkably in response to GMBs. These findings suggest that GMBs can effectively stimulate Fe(III) reduction in paddy fields, while simultaneously alleviating the pH increase usually caused by pristine biochar application.

Determination of zinc oxide content of mineral medicine calamine using near-infrared spectroscopy based on MIV and BP-ANN algorithm.

Near-infrared (NIR) spectroscopy has been widely used in the analysis fields of traditional Chinese medicine. It has the advantages of fast analysis, no damage to samples and no pollution. In this research, a fast quantitative model for zinc oxide (ZnO) content in mineral medicine calamine was explored based on NIR spectroscopy. NIR spectra of 57 batches of calamine samples were collected and the first derivative (FD) method was adopted for conducting spectral pretreatment. The content of ZnO in calamine sample was determined using ethylenediaminetetraacetic acid (EDTA) titration and taken as reference value of NIR spectroscopy. 57 batches of calamine samples were categorized into calibration and prediction set using the Kennard-Stone (K-S) algorithm. Firstly, in the calibration set, to calculate the correlation coefficient (r) between the absorbance value and the ZnO content of corresponding samples at each wave number. Next, according to the square correlation coefficient (r2) value to obtain the top 50 wave numbers to compose the characteristic spectral bands (4081.8-4096.3, 4188.9-4274.7, 4335.4, 4763.6,4794.4-4802.1, 4809.9, 4817.6-4875.4cm-1), which were used to establish the quantitative model of ZnO content using back propagation artificial neural network (BP-ANN) algorithm. Then, the 50 wave numbers were operated by the mean impact value (MIV) algorithm to choose wave numbers whose absolute value of MIV greater than or equal to 25, to obtain the optimal characteristic spectral bands (4875.4-4836.9, 4223.6-4080.9cm-1). And then, both internal cross and external validation were used to screen the number of hidden layer nodes of BP-ANN. Finally, the number 4 of hidden layer nodes was chosen as the best. At last, the BP-ANN model was found to enjoy a high accuracy and strong forecasting capacity for analyzing ZnO content in calamine samples ranging within 42.05-69.98%, with relative mean square error of cross validation (RMSECV) of 1.66% and coefficient of determination (R2) of 95.75% in internal cross and relative mean square error of prediction (RMSEP) of 1.98%, R2 of 97.94% and ratio of performance to deviation (RPD) of 6.11 in external validation.

Provenance, prevalence and health perspective of co-occurrences of arsenic, fluoride and uranium in the aquifers of the Brahmaputra River floodplain.

The present work focuses on understanding the provenance, prevalence and health perspective of As and F- along with possible co-occurrence of uranium (U) in the aquifers of the Brahmaputra floodplains (BFP), India. Groundwater (n = 164) and sediment samples (n = 5) were obtained from the upper, middle and lower BFP. Energy dispersive spectroscopy (EDX) revealed the presence of As, U and Fe in the sediment matrix. Regression analysis showed a weaker relationship between As and F- co-occurrence. Hierarchical cluster analysis (HCA) and principal component analysis (PCA) suggested reductive dissolution of Fe (hydr)oxides responsible for As release in the BFP, especially in the upper and lower BFP. Bicarbonate appeared to compete with As oxyanions for adsorption on positively charged surfaces leading to As release. Arsenic desorption in presence of PO43-, F- and HCO3- at elevated pH appeared greatest in the upper BFP, suggesting the highest potential for co-occurrence. Co-occurrence, were mainly in isolated aquifers of the upper BFP owing to desorption of adsorbed As and F- from Fe (hydr)oxides at higher pH. Weathering and dissolution of clay minerals in the upper BFP, and competitive desorption in presence of HCO3- and PO43- in the middle and lower BFP, respectively, explain variabilities in F- release. Amorphous Fe (hydr)oxides like ferrihydrite act as sinks of U. Concentrations of As and F- will likely increase in the future as projected from the saturated levels of goethite and ferrihydrite. Hazard indices (HI) revealed that children (3-8 years) were at greater health risk than adults.

Direct evidence for the enhanced acquisition of phosphorus in the rhizosphere of aquatic plants: A case study on Vallisneria natans.

There are few studies about the processes and mechanisms for aquatic plants to take up phosphorus (P) in wetland soils and sediments. Direct observation of P mobilization in rhizosphere is lacking. In this study, high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were used to capture the small-scale changes of soluble reactive P (SRP) and soluble Fe, and labile P in the rhizosphere of Vallisneria natans (V. natans), respectively. The results showed 5.92- and 3.12-fold enrichments of P and Fe in the Fe plaques formed on the root surfaces, respectively, in comparison with the P and Fe concentrations in the non-rhizosphere sediments. Moreover, simultaneous releases of P and Fe appeared in rhizosphere and the SRP concentration showed up to 114-fold increases compared to the non-rhizosphere sediments. Five kinds of low-molecular weight organic acids (LMWOAs) were detected in the root exudates; oxalic acid accounted for 87.5% of the total. Extraction of Fe and P in the Fe plaques was greatly enhanced by root exudates compared to deionized water, and oxalic acid contributed to 67% and 75% of the total extracted Fe and P, respectively. The coupling processes of Fe plaque enrichment of P and oxalic acid complexation of Fe(III) led to significantly enhanced P acquisition in the rhizosphere of V. natans.