Study of inorganic ligand-chromium(III)-surface ternary complexes by ESR spectroscopy

Cr(III) sorbed at the solid/water interface of latex and hectorite was studied by ESR spectroscopy in the presence of different inorganic ligands. The ESR spectra of the surface obtained in the presence of selenite, phosphate and fluoride can be explained in terms of ternary surface complex formation. This is contrasted by the behaviour of sulfate and selenate ions which were found to have no effect on the ligand field of Cr(III), either in the adsorbed state or in solution.     

The significance of surface complexation reactions in hydrologic systems: a geochemist's perspective

Complexation reactions at the mineral–water interface affect the transport and transformation of metals and organic contaminants, nutrient availability in soils, formation of ore deposits, acidification of watersheds and the global cycling of elements. Such reactions can be understood by quantifying speciation reactions in homogeneous aqueous solutions, characterizing reactive sites at mineral surfaces and developing models of the interactions between aqueous species at solid surfaces. In this paper, the application of thermodynamic principles to quantify aqueous complexation reactions is described. This is followed by a brief overview of a few of the methods that have been used to characterize reactive sites on mineral surfaces. Next, the application of empirical and semi-empirical models of adsorption at the mineral–water interface, including distribution coefficients, simple ion exchange models, and Langmuir and Freundlich isotherms is discussed. Emphasis is placed on the limitations of such models in providing an adequate representation of adsorption in hydrological systems. These limitations arise because isotherms do not account for the structure of adsorbed species, nor do they account for the development of surface charge with adsorption. This is contrasted with more sophisticated models of adsorption, termed ‘surface complexation models’, which include the constant capacitance model, the diffuse layer model, the triple layer model and the MUSIC model. In these models, speciation reactions between surface functional groups and dissolved species control the variable surface charge build-up and the specific adsorption properties of minerals in aqueous solutions. Next, the influence of mineral surface speciation on the reactivity of adsorbed species and on far from equilibrium dissolution rates of minerals is discussed. Finally, the applicability of microscopic models of surface complexation to field-scale systems is explored and the need to integrate sophisticated surface chemical and hydrological modeling approaches is stressed.     

Detoxification of Arsenite through Adsorption and Oxidative Transformation on Pyrolusite

Adsorption and oxidative transformation processes critically affect the mobility and toxicity of arsenic (As) in the environment. In this study, the detoxification of arsenite through adsorption and oxidation by pyrolusite was systematically investigated. Disappearance of aqueous As(III) in the solution can be efficiently achieved using pyrolusite. The As(III) oxidative transformation product arsenate or As(V) was obtained both in the solution and on the pyrolusite surface. The arsenic species adsorbed on pyrolusite exist in two forms: As(III) and As(V). Furthermore, over 64.8% of the adsorbed As cannot be desorbed. They were fixed more stably in the structure of the mineral to achieve a safer removal. Lower As(III) initial concentration increased As(III) detoxification rates. Elevating the reaction pH from 4.5 to 7.9 elicited a slight effect on the disappearance rate of As(III). Efficient As(III) detoxification can be achieved by pryrolusite within the studied pH range. The addition of low‐molecular‐weight carboxylic acids decreased the detoxification rate of As(III) through competition for active sites on pyrolusite. Co‐existing divalent metal ions, such as Ca²⁺, Ni²⁺, and Mn²⁺, also decreased the detoxification rate of As(III). However, the trivalent ion Cr³⁺ largely increased the detoxification rate through co‐precipitation and adsorption processes.     

Use of the Anion‐Exchange Resin Amberlite IRA‐93 for the Separation of Arsenite and Arsenate in Aqueous Samples

The method described uses the separation of As(III) and As(V) species in aqueous samples by means of the anion‐exchange resin Amberlite IRA‐93. The samples were acidified using acetic acid and passed through a glass column filled with pre‐treated Amberlite IRA‐93 resin. As(III) was poorly adsorbed on the anionic exchanger material, whereas As(V) was retained. The arsenic concentration was measured in the column effluent by graphite furnace AAS (GF‐AAS). The retained As(V) was eluted from the column using 1 M NaOH. Prior to the determination of the As(V) concentration in the NaOH eluate, the eluate was passed through a glass column filled with a cation‐exchange resin (Amberlite 200) to remove sodium ions and minimize the Na⁺ interference with the AAS determination. After calibration the method was applied to the separation of As(III) and As(V) species in two aqueous extracts of arsenic contaminated soils. The results were compared with those obtained from an on‐line separation and determination of As(III) and As(V) in the aqueous soil extracts using a state of the art HPLC‐ICP‐MS system.     

Adsorption of Chromium(III), Nickel(II), and Copper(II) from Aqueous Solution by Activated Alumina

The possible use of activated alumina powder (AAP) as adsorbent for Cr(III), Ni(II), and Cu(II) from synthetic solutions was investigated. The effect of various parameters on batch adsorption process such as pH, contact time, adsorbent dosage, particle size, temperature, and initial metal ions concentration were studied to optimize the conditions for maximum metal ion removal. Both higher (molar) and lower (ppm) initial metal ion concentration sets were subjected to adsorption on AAP. Adsorption process revealed that equilibrium was established in 50 min for Cr(III) at pH 4.70, 80 min for Ni(II) at pH 7.00, and 40 min for Cu(II) at pH 3.02. Percentage removal was found to be highest at 55°C for Cr(III) and Ni(II) with 420 µm and 45°C for Cu(II) with 250‐µm particle size AAP. A dosage of 2 g for Cr(III), 8 g for Ni(II), and 10 g Cu(II) gave promising data in the metal ion removal. The adsorption process followed Langmuir as well as Freundlich models. The thermodynamics of adsorption of these metal ions on activated aluminum indicated that the adsorption was spontaneous and endothermic in nature. Present study indicates that AAP can act as a promising adsorbent for industrial wastewater treatment.     

Experimental and modeling study on Cr(VI) transfer from soil into surface runoff

With the development of modern agriculture, large amount of fertilizer and pesticide outflow from farming land causes great waste and serious pollution to surface water and groundwater, and threatens ecological environment and even human life. In this paper, laboratory experiments are conducted to simulate adsorbed Cr(VI) transfer from soil into runoff. A two-layer in-mixing analytical model is applied to analyze laboratory experimental results. A data assimilation (DA) method via the ensemble Kalman filter (EnKF) is used to update parameters and improve modeling results. In comparison with the experimental data, DA updated modeling results are much better than those without the updating. To make predictions better, the inflation method with a constant inflation factor via DA method was used to compensate the fast decrease of ensemble spread partially related to filter inbreeding. Based on the used rainfall and relevant physical principles, the updated value of the incomplete mixing coefficient γ is about 14.0 times of the value of the incomplete mixing coefficient α in experiment 1 and about 7.4 times in experiment 2, while the difference between the flow rate of runoff and infiltration is not so large even after reaching stable infiltration condition. The results indicate the loss of Cr(VI) in soil solute is mainly due to infiltration, rather than surface runoff. With the increase of mixing layer depth, soil adsorption capacity will increase and the loss of soil solute will decrease. The study results provide information for reducing and even preventing the agricultural nonpoint source pollution.     

Biosorption of Cd(II), Ni(II) and Pb(II) from Aqueous Solution by Dried Biomass of Aspergillus niger: Application of Response Surface Methodology to the Optimization of Process Parameters

In this study, the biosorption of Cd(II), Ni(II) and Pb(II) on Aspergillus niger in a batch system was investigated, and optimal condition determined by means of central composite design (CCD) under response surface methodology (RSM). Biomass inactivated by heat and pretreated by alkali solution was used in the determination of optimal conditions. The effect of initial solution pH, biomass dose and initial ion concentration on the removal efficiency of metal ions by A. niger was optimized using a design of experiment (DOE) method. Experimental results indicated that the optimal conditions for biosorption were 5.22 g/L, 89.93 mg/L and 6.01 for biomass dose, initial ion concentration and solution pH, respectively. Enhancement of metal biosorption capacity of the dried biomass by pretreatment with sodium hydroxide was observed. Maximal removal efficiencies for Cd(II), Ni(III) and Pb(II) ions of 98, 80 and 99% were achieved, respectively. The biosorption capacity of A. niger biomass obtained for Cd(II), Ni(II) and Pb(II) ions was 2.2, 1.6 and 4.7 mg/g, respectively. According to these observations the fungal biomass of A. niger is a suitable biosorbent for the removal of heavy metals from aqueous solutions. Multiple response optimization was applied to the experimental data to discover the optimal conditions for a set of responses, simultaneously, by using a desirability function.     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Removal of Cr(VI) by Zero‐valent,Iron‐encapsulated Alginate Beads

Zero‐valent, iron‐encapsulated alginate beads were synthesized and were applied for the removal of Cr(VI) from aqueous solutions. The effects of several important parameters including solution pH, contact time, initial concentration and reaction temperature on Cr(VI) removal levels were investigated in batch studies. An initial solution pH of 1.0 was seen to be most favorable for Cr(VI) removal. The removal process was quick and almost 80% of the removal was attained within 60 min. The kinetic data followed the second‐order equation well. The Cr(VI) removal was almost reaction temperature‐independent and decreased with an increase in Cr(VI) initial concentration. The removal of Cr(VI) by iron‐encapsulated alginate beads was found to be significantly higher than that of non‐encapsulated alginate beads.     

Biopolymer-Based Nanocomposites for Removal of Cr(VI) from Aqueous Systems: A Review

Hexavalent chromium Cr(VI) has emerged as a contaminant of prime concern for the environmentalists because of its improper disposal by tannery, dye, and electroplating industries. Adsorption is the most exploited method for its removal from industrial wastewater because of its high removal efficiency even at low Cr(VI) concentration, minimal sludge, and ease of regeneration. In recent years, several adsorbents of biological origin such as plants, algae, fungi, and bacteria have been explored for Cr(VI) remediation. This review comprehends the recent studies involving usage of biopolymer-based nano-composites with respect to its adsorption mechanisms, adsorption capacities, isotherms, and kinetics. The conventional abiotic and biotic techniques for removal of Cr(VI) are also discussed with a comparative insight of their adsorption capacity and removal efficiency. Nano-biocomposites integrate the functional properties of both nanoparticles and biopolymers, which make them efficient biosorbents. Nano-biocomposites offer a large surface area, reduced particle loss, minimal particle agglomeration on the surface, and high stability. Common kinetic models among the nano-biocomposites,  and various equilibrium models are also analyzed to understand the mode of adsorption and associated factors. These materials are mostly found to follow monolayer adsorption with ion exchange, electrostatic interaction, and surface complexation as major players in the process.     

One river,two streams: chemical and chromium isotopic features of the Neglinka River (Karelia,northwest Russia)

The physico-chemical and hydrochemical characteristics of run-off of the Neglinka River Basin (northwest Russia) monitored for a year are different for the upstream and downstream sections. The river known hydrologically as the Neglinka, consists hydrochemically of two different streams: one represented by the upstream part of the basin, and the other one by the downstream. The upstream water is characterized by low mineralization (water hardness 0.08–0.43 mmol L^?1) and low δ⁵³Cr values (+0.30 to +0.42‰), whereas the lower part is characterized by high mineralization (water hardness 0.37–3.46 mmol L^?1) and high δ⁵³Cr values (+0.92 to +1.73‰). The difference in chemical composition of the upstream and downstream waters could be due to the underground discharge input. Aqueous chromium (Cr) mobilized from weathering profiles may have been reduced from soluble Cr(VI) to insoluble Cr(III) during the riverine transportation. Partial removal of Cr from the water balance resulted in a decrease in Cr concentration and an increase in δ⁵³Cr values.     

Toxicity assessments of nanoscale zerovalent iron and its oxidation products in medaka (Oryzias latipes) fish

Iron-based nanotechnologies are increasingly used for environmental remediation; however, toxicologic impacts of iron nanoparticles on the aquatic ecosystem remain poorly understood. We treated larvae of medaka fish (Oryzias latipes) with thoroughly characterized solutions containing carboxymethyl cellulose (CMC)-stabilized nanoscale zerovalent iron (nZVI), aged nanoscale iron oxides (nFe-oxides) or ferrous ion (Fe[II]) for 12-14 days' aqueous exposure to assess the causal toxic effect(s) of iron NPs on the fish. With the CMC-nZVI solution, the dissolved oxygen level decreased, and a burst of reactive oxygen species (ROS) was generated as Fe(II) oxidized to ferric ion (Fe[III]); with the other two iron solutions, these parameters did not significantly change. CMC-nZVI and Fe(II) solutions caused acute lethally and sublethally toxic effects in medaka larvae, with nFe-oxide-containing solutions causing the least toxic effects. We discuss modes of toxic action of iron NPs and chronic toxic effects in terms of hypoxia, Fe(II) toxicity and ROS-mediated oxidative damage.     

Speciation and spatial distribution of Cr in chromite ore processing residue site,Yunnan,China

Remediation of COPR sites requires the key information including chromium oxidation, speciation and spatial distribution. Samples were gathered from a COPR site in Luliang County in Qujing, Yunnan Province of China. The total Cr, Cr(VI) and chromium species were investigated. Results indicated the concentration of total Cr was between 110.5 and 21,774 mg/kg, and the concentration of Cr(VI) was between 0.1 and 1075 mg/kg. The map of total-Cr and ratio of Cr(VI)/total-Cr(%) showed that the maximum of total-Cr and Cr(VI) appeared in the layers near the surface. In the horizontal direction, the pollution was more serious in the middle and southeast part than that in the west. Additionally, acid extractable chromium increased in the layers at depth from-0.3 to-2.0 m, and it decreased in the deeper layers. There was a trend that the movable Cr(VI) migrated to the deeper layers, and then it turned into Cr(III). Water played an important role for the Cr distribution. Cr(VI) in COPR released to the soil solution after rainfall, and then gravity led the solution down to the deeper layers. After repeated rainfall and leaching,Cr(VI) moved to the deeper soil layers. Due to capillarity and evaporation, Cr(VI) migrated and was enriched at thesurface layer. Therefore, measures on controlling water movement should be taken in the remediation of the COPR site.     

The impact of four ethylene oxide–propylene oxide block copolymers on the surface tension of dispersions of soils and minerals in water

A comprehensive series of aqueous solutions of four ethylene oxide–propylene oxide–ethylene oxide block copolymers (EPE) of varying concentrations have been prepared. The EPE molecules are amphiphilic with the P blocks providing the hydrophobic segment of the molecules and the E blocks providing the hydrophilic parts. The surface tension of these solutions has been measured and compared with the surface tension of dispersions of soils (a clay soil and a sandy soil) and minerals (quartz–silica sand, bentonite and kaolinite) in the same aqueous solutions. It is observed that all the block copolymers reduce the surface tension of water; the extent to which it is reduced is determined by the surface activity of the EPE block copolymer, which in turn is related to the balance between the sizes of the P and E blocks. It is further observed that the in the presence of soil the surface tension increases as a result of block copolymer adsorption to the soil/water interface. The extent of adsorption appears to be related to the texture of the soil – the clay soil used in this investigation adsorbs more block copolymer than the sandy soil. In the presence of the mineral phases the surface tension reductions are variable. With bentonite the EPE block copolymers are completely adsorbed at low EPE concentrations as shown by surface tension values that are the same as those measured for pure water. Adsorption to kaolinite is limited and once the adsorption sites have been filled the surface tension of the aqueous phase is approaches the surface tension of the same solution without the presence of bentonite. On the other hand the silica sand is a poor adsorbent. Adsorption to the mineral phases is also dependent upon the relative hydrophobicity of the block copolymer. The more hydrophobic (as inferred by the critical micelle concentration) the copolymer the less readily it is adsorbed by the mineral phases. Thus relatively hydrophobic EPE block copolymers produce a relatively large decrease in surface tension and are less readily adsorbed by the soil and mineral phases. It is concluded that the presence of EPE block copolymers in soils can result in the drainage of soil water from the saturated zone as a result of surface tension reductions. However the extent of drainage is related to the surface activity/molecular composition of the EPE block copolymer; the textural class of the soil and the nature of the minerals present in the soil.     

Adsorption–Reduction Behavior of Co(NH3) on Activated Carbon

A novel method has been put forward to retrofit the wet ammonia desulfurization process to realize the combined removal of sulfur dioxide and nitric oxide by introducing soluble cobalt(II) salt into aqueous ammonia solution. The active constituent of scrubbing NO from the flue gases is the produced by ammonia coordinating with Co²⁺. The regeneration of can be realized under the catalysis of activated carbon so as to sustain a high NO removal efficiency for a long time. In this paper, the adsorption–reduction behavior of on activated carbon has been researched using scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy. A conclusion can be drawn from the results that cobalt ions in the aqueous solution are adsorbed by activated carbon and most of them are reduced to Co²⁺ ions, and some of the Co²⁺ ions are further reduced into metallic cobalt. The results also demonstrate that the functional groups on the surface of carbon take part in this redox reaction. The C? H groups on the carbon surface are oxidized into C? OH, and then some of the hydroxyl groups are further oxidized into carbonyl or carboxyl groups.     

Chromium(III) and Chromium(VI) Circulation in Aquatic Biocenoses

The cumulation of chromium(III) and (VI) has been studied in batch cultures of planktonic algae Microcystis incerta, Scedenesmus obliquus, Chlorella kessleri and Chlamydomonas geitleri at different chromium and algal cells concentrations. It has been found that chromium(VI) is practically not cumulated in algae, whereas chromium(III) is very rapidly cumulated in all types of algae investigated. The cumulation factor increases with the decrease of the radius of algae cells and it reaches the value of 10⁶ for Microcystis incerta even after a few hours of contact. The kinetics, the cumulation factors and the capacity of algae to cumulate chromium(III) is practically the same for living as well as for dead cells and therefore it can be concluded that the cumulation of chromium(III) is due predominantly to the chemical sorption on the surface of algal cells.     

Energy partitioning during seismic slip in pseudotachylyte-bearing faults (Gole Larghe Fault, Adamello, Italy)

The determination of the earthquake energy budget remains a challenging issue for Earth scientists, as understanding the partitioning of energy is a key towards the understanding the physics of earthquakes. Here we estimate the partition of the mechanical work density into heat and surface energy (energy required to create new fracture surface) during seismic slip on a location along a fault. Earthquake energy partitioning is determined from field and microstructural analyses of a fault segment decorated by pseudotachylyte (solidified friction-induced melt produced during seismic slip) exhumed from a depth of ~ 10 km—typical for earthquake hypocenters in the continental crust. Frictional heat per unit fault area estimated from the thickness of pseudotachylytes is ~ 27 MJ m^− 2. Surface energy, estimated from microcrack density inside clast (i.e., cracked grains) entrapped in the pseudotachylyte and in the fault wall rock, ranges between 0.10 and 0.85 MJ m^− 2. Our estimates for the studied fault segment suggest that ~ 97–99% of the energy was dissipated as heat during seismic slip. We conclude that at 10 km depth, less than 3% of the total mechanical work density is adsorbed as surface energy on the fault plane during earthquake rupture.     

From surface acidity to surface reactivity; inhibition of oxide dissolution

Paul Schindler's early work on the acid-base chemistry of oxides was instrumental for the development of the concept of surface complexation. This approach has not only been important in establishing a theory on the adsorption of metal ions and ligands as a function of pH and solution variables, but has become essential in establishing surface speciation (coordinative structural and electronic arrangement at the solidwater interface) which in turn determines surface reactivity. The factors that affect dissolution of Fe(III) (hydr)oxides and inhibition of dissolution are discussed. A few examples for the inhibition of reductive and ligand-promoted dissolution by binuclear complexes of oxoanions (phosphate, borate) and of protonpromoted dissolution by Cr(III) are given.     

Einfluß des Komplexbildungsgrades auf die Migrationsgeschwindigkeit von Eisen(II,III)-Verbindungen

This paper describes relations between the degree of complexation calculated with a mathematical model (FISCHER and REISSIG, 1984) and the ion-exchange and migration behaviour of iron(II, III)-compounds in a simulated aquifer. In general, the bonding of the complexes to the soil matrix becomes stronger with increasing positive charge. Negatively charged or neutral complex compounds do not show any, or show only slight interactions with the soil matrix. By complexation it is possible to achieve great differences in the migration behaviour of a particular metal. In the course of migration in the deposit there was found a separation of the complex mixture in accordance with charge. The break-through curves are characterized by a stepped shape, for this case. If weak acids or weak bases act as complex-forming ligands, the pH-dependent dissociation of the complexing species has to be taken into account in the complex calculation; this is represented by the example of the iron(III)-citrate system in this paper. Moreover, experimental results concerning the migration behaviour of iron(II, III)-fulvic acid complexes are given