Concentrations Of Organic Ligands Research Articles

Effects of oleylamine concentration on the synthesis of formamidinium lead halide perovskite nanocrystals and physical-optical properties

Perovskite nanocrystals (PNCs) has been extensively interested owing to their distinctive properties for applications in optoelectronics and energy harvesting. The properties of these nanocrystals, including optical and energy characteristics, can be tuned by adjusting the particle size using different synthesis techniques. Among these, the ligand-assisted reprecipitation (LARP) method has become popular for its simplicity and scalability. Nevertheless, it is vital to understand that the growth of PNCs is extremely sensitive to the conditions of synthesis, highlighting the importance of recognizing the factors that limit the formation and properties of PNCs. In this study, PNCs based on formamidinium lead bromide (FAPbBr3) were synthesized via the LARP method under room temperature and ambient atmospheric conditions. The structures and optical properties, including photoluminescence lifetime, of PNCs with varying amounts of organic ligands were investigated. Transmission electron microscopy showed that high concentrations of organic ligands lead to the formation of perovskite clusters. We also noted a slight red shift in the photoluminescence peak as the size of the PNCs increased. A peak photoluminescence quantum yield (PLQY) of 74% was achieved. This study provides crucial insights into the effects of ligand ratios and serves as a valuable resource for refining the synthesis parameters of PNCs.

Controlled synthesis of defective MOF-808 and its application in levulinic acid esterification

Defective MOF-808 (Def. MOF-808) plays a pivotal role in catalysis, offering the potential for optimizing catalytic reactions and enhancing reactivity. Through precise control of MOF-808 synthesis conditions, including time, temperature, zirconium (Zr) source, ligand ratio, defect agent type, and content, we systematically studied their effect on material properties. The results showed that by adjusting these conditions, we synthesized a series of MOF-808 materials with varying defect concentrations, referred to as Def. MOF-808. Shorter synthesis times, lower temperatures, defect agents with stronger coordination capabilities, and increased defect agent concentration or reduced organic ligand concentration effectively enhance Def. MOF-808’s defect concentration. The presence of defect sites facilitates the effective binding of the sulfate group, thereby amplifying the level of sulfation and augmenting its acid catalytic potential. Furthermore, this study unveiled a direct link between defect concentration and the catalytic activity observed in the levulinic acid esterification reaction. The Defect-engineered MOF-808 optimized through response surface design demonstrates exceptional heterogeneous acid catalysis performance, achieving impressive conversion rates of 97.5% and selectivity of 96.2%, coupled with remarkable catalytic stability. This study highlights defect engineering as a successful strategy to improve MOF-808 catalyst performance, offering insights for future enhancements.

The importance of the soluble and colloidal pools for trace metal cycling in deep-sea pore waters

Physical and chemical trace metal speciation are important for our understanding of metal cycling and potential toxicity to marine life. Trace metals can behave differently in diffusion processes or particle-solution interactions and have different bioavailabilities depending on their physical and chemical forms, which often depend on redox conditions. Here we investigated dissolved (< 0.2 µm) and soluble (< 0.02 µm) concentrations of Mn, Co, Ni, Fe, Cu, V, Mo, U, Cd, and As in oxic and suboxic deep-sea sediments of the central equatorial Pacific Ocean. Vanadium, Mo, U, As, and Cd showed no significant concentration differences between their dissolved and soluble forms, suggesting that they are present as inorganic ionic species or organic complexes in the truly dissolved or small colloidal fraction. In contrast, the colloidal fraction (> 0.02 µm < 0.2 µm) of Mn, Co, Ni, and Cu increased with depth in oxic pore waters and Fe had the largest but variable colloidal pool. Soluble Mn, Co, and Ni were released in the uppermost 2-4 cm in the sediment because of reductive dissolution. The increasing colloidal fraction with depth suggests a decrease in the concentration of small organic ligands with depth, that are abundant in the surface sediment pore waters, and instead an increasing importance of larger (> 0.02 µm) inorganic nanoparticles and colloids such as Mn and Fe (oxyhydr)oxides that control Mn, Fe, and Co cycling at depths > 10 cm. The distribution of Ni and Cu cannot be exclusively explained by inorganic nanoparticles and a shift from low to larger high molecular weight organic ligands might occur. These findings provide new insights into trace metal distributions in the dissolved phase, highlighting the diversity of metal complexes and the need to incorporate these in future calculations of benthic metal fluxes and ecotoxicity assessments, especially in oxic pore waters.

Recommendations for best practice for iron speciation by competitive ligand exchange adsorptive cathodic stripping voltammetry with salicylaldoxime

The method of competitive ligand exchange followed by adsorptive cathodic stripping voltammetry (CLE-AdCSV) allows for the determination of dissolved iron (DFe) organic speciation parameters, i.e., ligand concentration (LFe) and conditional stability constant (log KFe′Lcond). Investigation of DFe organic speciation by CLE-AdCSV has been conducted in a wide range of marine systems, but aspects of its application pose challenges that have yet to be explicitly addressed. Here, we present a set of observations and recommendations to work toward establishing best practice for DFe organic speciation measurements using the added ligand salicylaldoxime (SA). We detail conditioning procedures to ensure a stable AdCSV signal and discuss the processes at play during conditioning. We also present step-by-step guidelines to simplify CLE-AdCSV data treatment and interpretation using the softwares ECDSoft and ProMCC and a custom spreadsheet. We validate our application and interpretation methodology with the model siderophore deferoxamine B (DFO-B) in a natural seawater sample. The reproducibility of our application and interpretation methodology was evaluated by running duplicate titrations on 19 samples, many of which had been refrozen prior to the duplicate analysis. Nevertheless, 50% of the duplicate analyses agreed within 10% of their relative standard deviation (RSD), and up to 80% within 25% RSD, for both LFe and log KFe′Lcond. Finally, we compared the sequential addition and equilibration of DFe and SA with overnight equilibration after simultaneous addition of DFe and SA on 24 samples. We found a rather good agreement between both procedures, with 60% of samples within 25% RSD for LFe (and 43% of samples for log KFe′Lcond), and it was not possible to predict differences in LFe or log KFe′Lcond based on the method applied, suggesting specific association/dissociation kinetics for different ligand assemblages. Further investigation of the equilibration kinetics against SA may be helpful as a potential way to distinguish natural ligand assemblages.

Sorption Behavior of Radionuclides on Engineered and Natural Barriers and Prediction of Sorption Distribution Coefficients Using Support Vector Regression

A low- and intermediate-level radioactive waste repository contains various types of radionuclides and organic complexing agents. Their chemical interaction within the repository can lead to the formation of radionuclide-ligand complexes, influencing the limited retention behaviors of radionuclides. This study focuses on the sorption behavior of radionuclides on both engineered (concrete) and natural barriers (sedimentary rock and granite), as well as the prediction of sorption distribution coefficients (Kd) using support vector regression. Batch studies were conducted to determine the K d values for three radionuclides (99Tc, 137Cs, and 238U) under different conditions, including pH, temperature, and the presence of organic ligands (such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and isosaccharinic acid). The K d values for 238U exhibited a sharp decrease with increasing concentrations of organic ligands. In contrast, the K d values for 99Tc showed only a slight reduction at higher organic ligand concentrations. Meanwhile, the K d values for 137Cs remained relatively unchanged, regardless of the type and initial concentration of organic ligands. This suggests a high level of retention for 137Cs in the rock samples. The support vector regression model with a radial basis kernel function proved effective in predicting the K d values under different experimental conditions. This enhancement in predicting accuracy contributes valuable insights into understanding the sorption processes involved in radionuclide behavior. Overall, this study advances our knowledge of radionuclide behavior on both engineered and natural barriers while providing a reliable prediction tool for estimating sorption distribution coefficients.

Trace metal dissolution kinetics of East Asian size-fractionated aerosols in seawater: The effect of a model siderophore

Aerosol soluble metals are considered bioavailable to marine phytoplankton and may influence phytoplankton growth, their community structure, and material cycling in the ocean. The dissolution is controlled by the physical and chemical properties of aerosols and various atmospheric, physical, and biogeochemical processes before and after depositing in the surface water. Among these complicated processes, the interaction of aerosol metals with organic ligands in seawater is one of the major factors. In this study, we systematically investigated the dissolution kinetics of trace metals from fine (0.45–0.95 μm) and coarse (>7.2 μm) aerosols in seawater for 30 days under conditions with or without adding a model Fe organic ligand, siderophore desferrioxamine B (DFB). We found that most of the soluble metals in the fine aerosols were leached rapidly within the first hour. In terms of the coarse aerosols, with DFB addition, the fractional solubility of Fe increased substantially from 0.1 to 10%, and the solubilities of most other metals generally increased by about 2-fold within 30 days. Without DFB addition, we found that most soluble metals were still gradually released over time in coarse aerosols, except particle-reactive metals, Fe and Pb. We further observed strong linear correlations between dissolved metals (Al, Fe, Mn, Co, Ni, and Zn) and silicate concentrations for DFB addition with coarse aerosols, with metal to silicate ratios comparable to those of typical aluminosilicates. Quantitatively, the aluminosilicate-associated dissolved metals accounted for >85% of total dissolved Fe, Al, and Co, and 40–60% for total dissolved Mn and Ni with the addition of DFB for 30 days. By comparing dissolved metal to Al ratios with lithogenic ratios, the metals leached in the first hour for both coarse and fine aerosols originated from anthropogenic sources, and lithogenic aerosols gradually became the dominant soluble metal source for coarse aerosols after 1 h, extending to 720 h. The findings of this study exhibit the importance of the time-dependent interaction of lithogenic aerosols with organic ligands in seawater. The residence time of aerosol particles and the concentrations of available organic ligands in the euphotic zone are key factors affecting aerosol dissolved metal availability to marine phytoplankton in the surface ocean.

Synthesis, characterization, biological activity, DFT studies on transition metal complexes derived from 5,5′-(propane-1,3-diylbis(sulfanediyl))bis(1,3,4-thiadiazol-2-amine) ligand and its corrosion inhibition study on carbon steel

The goal of our research was to create new ligand-metal complexes that could be characterized using various physicochemical techniques like elemental analyses, molar conductivity, magnetic susceptibility, infrared (IR), electronic absorption, 1H NMR, mass spectral studies and thermal analysis. The analytical data and mass spectra of the ligand and the complexes confirm the stoichiometry of metal complexes as being of the metal to ligand ratio is 1:1. The magnetic measurements and spectral studies evidenced the octahedral geometry of the complexes. The ligand was found to be neutral tetradentate and coordinated to the metal ions in NNSS mode via the two-amine nitrogen and two sulfur atoms as revealed from the IR spectral studies. The decomposition of the ligand and the complexes were discussed according to the data obtained from thermogravimetric analysis within the temperature range from room temperature to 1000 °C. The antimicrobial, antioxidant and anticancer assay have been explored and the minimum inhibitory concentration (both liquid and Disc method) of organic ligand and its metal complexes against various microbial pathogens were reported. Most of the metal complexes showed comparable activities and, in some cases, greater activity against tested organisms. Ni(II) (26.7±0.6 mm/mg), Ni(II) (30.0±1.0 mm/mg), Cd(II) (30.3±0.6 mm/mg) and Ni(II) (21.3±0.6 mm/mg) complexes had the highest activity against Escherichia coli, Klebsiella pneumonia, Staphylococcus aureus and Streptococcus mutans organisms even better than the standards. The Cu(II) (IC50 = 6.49 µg/mL) and Cd(II) (IC50 = 7.62 µg/mL) complexes showed the highest anticancer effect than the other complexes. The results showed the superior activity of the complexes over the ligand in accordance with the chelation theory. The inhibition activity of ligand was studied in acid medium used by impedance spectroscopy (EIS), electrochemical frequency modulation (EFM), and electrochemical potentiodynamic polarization (PDP), and the results obtained evidenced the success of the ligand for inhibiting the corrosion of steel.

The distribution and speciation of dissolved Cd and Pb in the Bohai Sea and Yellow Sea, China

The speciation of dissolved trace metals is important due to its closely linkage with toxicity and bioavailability in seawater. We investigate the speciation of dissolved Pb (DPb) and Cd (DCd), and their spatial distributions in the Yellow Sea and Bohai Sea, China. The results showed that the organic complexation of DPb and DCd accounted for 35 ± 14 % and 75 ± 10 % of their dissolved concentrations, respectively. The measured free ion activity of Cd ({Cd2 +}) and organic ligand concentration of Cd ([LCd]) were highest near the Yellow River mouth, where the free ion activity of Pb ({Pb2+}) were also found to be the highest. In this study, both {Pb2+} and {Cd2+} did not exceed the toxicity threshold, and they were identified not toxic in the waters of the Yellow Sea and Bohai Seas, but biological accumulation effects potentially exist.

Fe-binding organic ligands in coastal and frontal regions of the western Antarctic Peninsula

Abstract. Organic ligands are a key factor determining the availability of dissolved iron (DFe) in the high-nutrient low-chlorophyll (HNLC) areas of the Southern Ocean. In this study, organic speciation of Fe is investigated along a natural gradient of the western Antarctic Peninsula, from an ice-covered shelf to the open ocean. An electrochemical approach, competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV), was applied. Our results indicated that organic ligands in the surface water on the shelf are associated with ice-algal exudates, possibly combined with melting of sea ice. Organic ligands in the deeper shelf water are supplied via the resuspension of slope or shelf sediments. Further offshore, organic ligands are most likely related to the development of phytoplankton blooms in open ocean waters. On the shelf, total ligand concentrations ([Lt]) were between 1.2 and 6.4 nM eq. Fe. The organic ligands offshore ranged between 1.0 and 3.0 nM eq. Fe. The southern boundary of the Antarctic Circumpolar Current (SB ACC) separated the organic ligands on the shelf from bloom-associated ligands offshore. Overall, organic ligand concentrations always exceeded DFe concentrations (excess ligand concentration, [L′] = 0.8–5.0 nM eq. Fe). The [L′] made up to 80 % of [Lt], suggesting that any additional Fe input can be stabilized in the dissolved form via organic complexation. The denser modified Circumpolar Deep Water (mCDW) on the shelf showed the highest complexation capacity of Fe (αFe'L; the product of [L′] and conditional binding strength of ligands, KFe'Lcond). Since Fe is also supplied by shelf sediments and glacial discharge, the high complexation capacity over the shelf can keep Fe dissolved and available for local primary productivity later in the season upon sea-ice melting.

Spatial and temporal variability of dissolved aluminum and manganese in surface waters of the northern Gulf of Alaska

The Northern Gulf of Alaska (NGA) shelf is a productive high-latitude environment where nutrient dynamics are greatly impacted by the seasonal variability in freshwater input. Iron is a key nutrient on the NGA shelf that directly modulates primary production, and freshwater is a major input of iron to the NGA shelf. However, variability in the input of dissolved iron from freshwater sources is obscured by high biological uptake and by the concentration of organic ligands, which bind iron and help maintain it in solution. Riverine inputs of other lithogenic elements such as aluminum and manganese are expected to behave quasi-conservatively on the NGA shelf and could help provide insight into the variability of iron input in this region.Here we present the seasonal (spring, summer, and fall) distribution of dissolved aluminum (dAl) and manganese (dMn) observed during 2018 and 2019 in the NGA region. Data were obtained during the NGA Long Term Ecological Research (LTER) site cruises and include several surface transects from Kayak Island to Kodiak Island, vertical profiles at several locations sparsely distributed throughout the shelf, and surface information from a Copper River plume study. We find that seasonal patterns in the surface concentrations of dMn and dAl mirrored annual glacial melt cycles, with the lowest values observed in spring and higher values in summer and fall. Sharp cross-shelf gradients were observed for both metals particularly in summer and fall. Surface concentrations decreased (by 1–2 orders of magnitude) away from the outflow of the Copper River, the major point source of freshwater within the NGA LTER site. Extremely high concentrations in the Copper River plume (≤1395 nM dAl, ≤128 nM dMn) and strong correlations with salinity (p = 7.9E-14 for dAl, 1.4E-14 for dMn) highlight the quasi-conservative nature of these metals within the plume. Enhanced dAl and dMn concentrations within nepheloid layers in subsurface waters indicate regions where a sedimentary source of iron could also be important. Residence times for dAl and dMn in surface waters over the NGA shelf were estimated to be 31 days (dAl) and 42 days (dMn) on average based on summer and fall data from both years.

The role of gentisic acid on the Fe(III) redox chemistry in marine environments

Phenolic compounds excreted by marine microalgae are part of the ligand pool in natural waters. The effect of the polyphenol gentisic acid (GA; 2,5 dihydroxybenzoic acid) on the Fe(III) reduction as a function of organic ligand concentration (100 nM – 1000 nM) and the pH (7.00–8.01) was investigated in seawater. Major seawater ions interactions with both GA and Fe(III) were also considered using 0.7 M NaCl +2 mM NaHCO3 solutions with each major ions (Mg2+, Ca2+, SO42−, K+, F−, Sr2+) at the same ratio than that in a 35 salinity seawater. The Fe(III)-GA complex in solution was able to produce Fe(II) in a pH-dependent process that was faster in seawater than in NaCl-NaHCO3 solution. The addition of each major ion affected the Fe(III) reduction process. At pH 7.5, the presence of Mg2+ and Ca2+ contributes to accelerate the reduction rate constant of Fe(III) to Fe(II). The K+, F−, Sr2+, and SO42− ions slow down the Fe(III) reduction rate constant. At pH 7.8, the effect of the ions is counteracted. Increasing the pH to 8, the effect on the solubility of Fe(III) is more important, being greater in NaCl and no reduction of Fe(III) was detected, compared with seawater.In this study, the formation and dissociation of the Fe(III)-GA complex in seawater was studied, resulting in kf = 1.19(±0.18)•104 (M−1 s−1), kd = 1.86 (±0.53)•10−4 (s−1), and conditional complexation constant of logKFe3+LCond = 17.81 ± 0.05 in seawater.Accordingly, phenolic compounds like GA influence the Fe marine biogeochemical cycles promoting the formation of the bioavailable Fe(II) in solution. Taking this into account, the Fe(III) reactions with phenolic compounds have to be considered to improve our understanding of the global iron cycle.

Impact of selected cement additives and model compounds on the solubility of Nd(III), Th(IV) and U(VI): screening experiments in alkaline NaCl, MgCl2 and CaCl2 solutions at elevated ionic strength

Abstract The solubility of Nd(III), Th(IV) and U(VI) was studied from undersaturation conditions in the presence of selected organic cement additives and model compounds: adipic acid, methyl acrylate, citric acid, melamine, ethylene glycol, phthalic acid and gluconic acid. Experiments were performed under Ar atmosphere in NaCl (2.5 and 5.0 M), MgCl2 (1.0 and 3.5 M) and CaCl2 (1.0 and 3.5 M) solutions with 9 ≤ pHm ≤ 13 (pHm = −log[H+]). Initial concentrations of organic ligands in solution were set constant in all systems to [L]0 = 0.025 M, except in specific cases (e.g. adipic acid, melamine and phthalic acid) where the ligand concentration in the matrix solutions was lower and controlled by solubility. Adipic acid, methyl acrylate, melamine, ethylene glycol and phthalic acid do not impact the solubility of Nd(III), Th(IV) and U(VI) in the investigated NaCl, MgCl2 and CaCl2 systems. Citrate significantly enhances the solubility of Nd(III), Th(IV) and U(VI) in NaCl systems. A similar effect was observed for Th(IV) and U(VI) in the presence of gluconate in NaCl systems. The impact of pH on the stability of the complexes is different for both ligands. Because of the larger number of alcohol groups in the gluconate molecule, this ligand is prone to form more stable complexes under hyperalkaline conditions that likely involve the deprotonation of several alcohol groups. The complexation of gluconate with U(VI) at pHm ≈ 13 is however weaker than at pHm ≈ 9 due to the competition with the highly hydrolysed moiety prevailing at pHm ≈ 13, i.e. UO2(OH)4 2−. The impact of citrate and gluconate in MgCl2 and CaCl2 systems is generally weaker than in NaCl systems, expectedly due to the competition with binary Mg-L and Ca-L complexes. However, the possible formation of ternary complexes further enhancing the solubility is hinted for the systems Mg/Ca-Th(IV)-GLU and Ca-U(VI)-GLU. These observations reflect again the differences in the complexation properties of citrate and gluconate, the key role of the alcohol groups present in the latter ligand, and the importances of interacting matrix cations. The screening experiments conducted within this study contribute to the identification of organic cement additives and model compounds potentially impacting the solution chemistry of An(III)/Ln(III), An(IV) and An(VI) under intermediate to high ionic strength conditions (2.5 ≤ I ≤ 10.5 M). This shows evident differences with respect to investigations conducted in dilute systems, and thus represents a very relevant input in the safety assessment of repositories for radioactive waste disposal where such elevated ionic strength conditions are expected.

Varying the Concentration of Organic Acid and Amine Ligands Allows Tuning between Quantum Dots and Magic-Sized Clusters of CH3NH3PbBr3 Perovskite: Implications for Photonics and Energy Conversion

Metal halide perovskites, such as methylammonium lead halide (CH3NH3PbBr3), have recently attracted tremendous attention due to their outstanding properties and promising applications. Here, CH3NH3...

In-situ HKUST-1 growth into inner pores of activated carbon granule for CO2 efficient capture

Metal-organic frameworks (MOFs) are efficient adsorption materials for carbon capture and storage. We proposed a strategy of solid-liquid in-situ reaction method to grow MOFs in activated carbon granule (AC), preparing high efficient CO2 adsorbent. At first, metal salts were solidified in the pores of AC granule carriers by 445 K treating. Then the organic ligands were introduced into the pores of AC. The MOF can be successfully prepared by solidliquid reaction method. By this method, MOFs uniformly disperse in AC pores, making it possible for MOFs used in fixed bed adsorption separation. The CO2 adsorption was tested by conducting breakthrough experiments in a fixed bed. When organic ligand concentration increased from 0 to 6%, the CO2 uptake value increased from 0.2868 mmol⋅g−1 to 0.3324 mmol⋅g−1 in the CO2/Air atmosphere with CO2 concentration of 10%. The CO2 uptake value increased 67% at 5000 PPM compared to original AC.

Formation of Metal-Organic Frameworks on a Metal Ion-Doped Polymer Substrate: In-Depth Time-Course Analysis Using Scanning Electron Microscopy.

The growth of metal-organic frameworks (MOFs) on a metal ion-doped polymer as a precursor and support substrate was investigated based on mechanistic and kinetic analyses. The studies were performed by varying the reaction temperature and the concentrations of the organic ligand and nucleation-promoted additive. Using the NH2-MIL-53(Al) framework as a model system, a systematic study of the mechanism of formation of tetragonal- and rod-shaped NH2-MIL-53(Al) crystals on the substrate was performed. The nucleation rate in the early stage of the reaction is a major factor in determining the surface morphology of the resultant NH2-MIL-53(Al) crystal films, as confirmed by changing the concentration of organic ligands and by employing pyridine additives. These results provide a fundamental understanding of the influence of the nucleation rate on the ability to control the morphology and structure of MOF crystal films.

The organic complexation of iron in the Ross sea

The Ross Sea Polynya (RSP) has the highest primary production of Antarctic waters. Iron (Fe) is one of the most important growth limiting factors in the Southern Ocean. Dissolved iron (DFe)-binding organic ligands play an important ecological role because they increase the residence time of the scarce Fe. Therefore, we studied the DFe-binding organic ligands in the vicinity of the Ross Sea during a cruise between 20 December 2013 and 5 January 2014. The DFe-binding organic ligands were measured using Competing Ligand Exchange Cathodic Stripping Voltammetry (CLE-CSV) with TAC as competing ligand. The DFe-binding organic ligand concentrations always exceeded the DFe concentrations except in the bottom nepheloid layer of the RSP. No relationship was found between depth and DFe-binding organic ligand concentrations in the RSP indicating that these ligands are resistant to degradation and are probably exported by high salinity shelf water into the circumpolar current. DFe-binding organic ligand concentrations were highest in the RSP and the Antarctic Circumpolar Current (ACC) west of the Ross Sea, in association with seasonal phytoplankton blooms, although no correlation was found with parameters reflecting phytoplankton abundance or species. Phytoplankton sources and sinks of DFe-binding organic ligands are likely related to the seasonal progression of the bloom. In 39% of the samples, two DFe-binding organic ligand groups were distinguished based on the difference in binding strength. The distinction was especially clear in the RSP and in the ACC west of the RSP (54 and 77% of the samples, respectively) where blooms occurred and much less in the low biomass waters of the ACC east of the RSP and ice covered eastern part of the Ross Sea (15 and 10% of the samples, respectively). In these waters, other environmental factors, like sea ice melt, probably explain the absence of distinct relationships between primary production and ligand characteristics.

Distribution and speciation of copper and its relationship with FDOM in the East China Sea

Total dissolved Cu concentrations, concentrations and conditional stability constants of Cu-binding organic ligands, and the intensities of fluorescent dissolved organic matter (FDOM) components in seawater were determined in the East China Sea. Concentrations of organic ligands were determined using CLE-AdCSV with a 5 μM SA detection window. Total dissolved Cu concentrations ranged from 0.59 nM to 4.65 nM and were particularly high in surface waters with low salinity due to influences of the Changjiang Diluted Water. Concentrations of the stronger ligand (L1) were between 0.65 and 6.92 nM and its distribution closely followed that of dissolved Cu. Four FDOM components were detected in surface waters, including two humic-like and two protein-like components. L1 concentrations exhibited similar distribution patterns to the intensities of all four FDOM components. The concentrations of the weaker ligands (L2) ranged from 2.86 nM to 31 nM, with the highest concentrations detected in the surface waters of stations unaffected by the Kuroshio Current. We found the buffering ability of Cu-binding organic ligands in the East China Sea to be sufficient for responding to atmospheric and anthropogenic Cu inputs and keeping the free cupric ion concentrations relatively constant.

A multivariate analysis of health risk assessment, phytoremediation potential, and biochemical attributes of Spinacia oleracea exposed to cadmium in the presence of organic amendments under hydroponic conditions

Cadmium (Cd) phytoremediation potential and its accumulation in edible and nonedible plant tissues is the function of various biochemical processes taking place inside plants. This study assessed the impact of organic ligands on Cd phyto uptake and different biophysiochemical processes of Spinacia oleracea L., and associated health hazards. Plants were exposed to Cd alone and chelated with citric acid (CA) and ethylenediaminetetraacetic acid (EDTA). Results revealed that the effect of Cd on lipid peroxidation, H2O2 production and pigment contents varied greatly with its applied level and the type of organic ligand. Moreover, the effect was more prominent in root tissues than leaf tissues and for high concentrations of Cd and organic ligands. Cadmium accumulation increased by 90 and 74% in roots and leaves, respectively, with increasing Cd levels (25–100 µM). Cadmium exposure at high levels caused lipid peroxidation in roots only. Application of both CA and EDTA slightly diminished Cd toxicity with respect to pigment contents, lipid peroxidation and hydrogen peroxide (H2O2) contents. Hazard quotient (HQ) of Cd was <1.00 for all the treatments. Under nonlinear effect of treatments, multivariate analysis can be an effective tool to trace overall effects/trends.

Revised Pourbaix diagrams for the vanadium – water system

The forms of occurrence of vanadium metal are determined by the major chemical reactions in the aquatic environment such as hydrolysis, oxidation, reduction, and precipitation. Depending on pH, potential and total concentration of inorganic ions and organic ligands, vanadium compounds may undergo various transformations to produce a whole range of chemical forms in aqueous systems. In this paper, a novel approach has been applied for calculating potential-pH (Pourbaix) diagrams, based on the developed thermodynamic analysis of chemical equilibria in the V–H2O system. On the basis of currently revised thermodynamic data for V(III), V(IV) and V(V) hydrolysis and original thermodynamic and graphical approach used, the repartition of their soluble and insoluble chemical species has been investigated. By means of ΔG–pH diagrams, the areas of thermodynamic stability of V(IV) and V(V) hydroxides have been established for a number of analytical concentrations of vanadium in heterogeneous mixtures. The obtained results, based on the thermodynamic analysis and graphic design of calculated data, are in good agreement with available experimental data.

Biological Characteristics and Concentrations of Extractable Fe, Al, and Si Compounds in Spruce Rhizosphere in Podzolic Soil

Some biological properties and concentrations of extractable Fe, Al, and Si compounds in the samples of the AOEL horizon of podzolic soil taken in five replicates from the rhizosphere of 15- to 20-year-old spruce and from the nonrhizosphere soil are discussed. The soil mass of the rhizosphere is characterized by a significantly higher total number of bacteria, more abundant and diverse saprotrophic bacterial complex, greater length of fungal mycelium, and higher content of benzenecarboxylic acids dominated by benzoic acid in comparison with the nonrhizosphere soil. The soil mass of the rhizosphere and the fraction of 1–5 µm isolated from it are also characterized by significantly higher concentrations of Fe and Al extracted by the Tamm and Bascomb reagents because of the accumulation of Fe-organic and Al-organic complexes. For extractable Al compounds in the rhizosphere, this finding is confirmed by the high coefficient of correlation between the amount of Al in the extracts and the Corg content in the bulk soil mass and in the fraction 1–5 µm. Such a correlation is absent in the nonrhizosphere soil. The content of iron compounds extracted by the Mehra–Jackson reagent from the rhizosphere and nonrhizosphere soils is significantly higher than that extracted by the Tamm and Bascomb reagents; in the nonrhizosphere samples, it is significantly higher than in the rhizosphere. This difference can be explained by the fact that the content of Fe oxides and hydroxides minerals decreased in the soil mass of the rhizosphere due to more active dissolution processes under the conditions of more acid medium and higher concentration of organic ligands, so that the mobilized Fe enters Fe–organic complexes.