Impedance investigation of the mechanism of copper electrodeposition from acidic perchlorate electrolyte

The mechanism of the copper electrodeposition from acidic perchlorate electrolyte has been investigated with polarization and impedance methods. The impedance of the copper electrode in copper perchlorate electrolytes has been measured as a function of frequency for different Edc overpotential values and different copper(II) ion concentrations. The relations between the shape of a complex plane impedance display and the copper electrode potential values as well as the concentration of CuII ion were analysed in terms of the electrode reaction mechanism. It is shown, that the presence of the intermediate cuprous ion and its sinusoidal change of transport rate is one of the main factors determining the depressed shape of the impedance arc. The quantitative relation between the faradaic impedance and the rates of electrode reaction rates was established. The impedance arc was simulated with a set of parameters involving: rate constants, Tafel slopes, diffusion coefficient of cuprous ion and double layer capacitance. The rate constants were calculated with respect to ECu2 + Cu00 as: k10 = 6.50 × 10−5 cm s−1, k20 = 0.139 cm s−1, k−20 = 1.88 × 10−7 mol cm−2 s−1.     

Activation of glassy carbon electrodes by photocatalytic pretreatment

This paper describes a simple and rapid photocatalytic pretreatment procedure that removes contaminants from glassy carbon (GC) surfaces. The effectiveness of TiO₂ mediated photocatalytic pretreatment procedure was compared to commonly used alumina polishing procedure. Cyclic voltammetric and chronocoulometric measurements were carried out to assess the changes in electrode reactivity by using four redox systems. Electrochemical measurements obtained on photocatalytically treated GC electrodes showed a more active surface relative to polished GC. In cyclic voltammograms of epinephrine, Fe(CN)₆^3−/4− and ferrocene redox systems, higher oxidation and reduction currents were observed. The heterogeneous electron transfer rate constants (k^o) were calculated for Fe(CN)₆^3−/4− and ferrocene which were greater for photocatalytic pretreatment. Chronocoulometry was performed in order to find the amount of adsorbed methylene blue onto the electrode and was calculated as 0.34 pmol cm⁻² for photocatalytically pretreated GC. The proposed photocatalytic GC electrode cleansing and activating pretreatment procedure was more effective than classical alumina polishing.     

Polymeric ternary metal thiols I. Products from reaction of Cu(II) with MoS4

The black, polymeric, product isolated from the reaction of Cu(II) salts with MoS₄²⁻ has been shown to have some unexpected and unusual properties, i.e. a stoichiometry of Cu_1.6MOS₄X_y (X = Cl⁻, Br⁻, y ≈ 1; X = SO₄²⁻, y ≈ 0.5), reduction of the metal centres to Cu(I) and Mo(V), the presence of S radical centres, and the absorption of ca. 2 mol O₂. EXAFS spectra have also been recorded. The W anion WS₄²⁻ behaves identically.     

Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-Co^IITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-Co^IITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-Co^IITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to Co^III/Co^II and Co^IIIPc⁻¹/Co^IIIPc⁻². The surface coverage (Γ) value, calculated by integrating the charge under Co^II oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-Co^IITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-Co^IITAPc on GC electrode has reached the saturation coverage (Γ_s) within 3 h. The Γ_s value for the SAM of 4α-Co^IITAPc on GC electrode was found to be 2.37 × 10⁻¹⁰ mol cm⁻². Gibbs free energy (ΔG_ads) and adsorption rate constant (k_ad) for the adsorption of 4α-Co^IITAPc on GC surface were found to be −16.76 kJ mol⁻¹ and 7.1 M⁻¹ s⁻¹, respectively. The possible mechanism for the self-assembly of 4α-Co^IITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-Co^IITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-Co^IITAPc is adopting nearly a flat orientation or little bit tilted orientation.     

In situ STM studies of Ga electrodeposition from GaCl3 in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide

In the present paper the electrodeposition of Ga on Au(1 1 1) from 0.5 mol L⁻¹ GaCl₃ in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py_1,4]TFSA, has been investigated by in situ scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and cyclic voltammetry (CV). The CV shows two redox processes: the one at −0.3 V vs. Pt is attributed to a Ga deposition on a Ga layer formed during an electroless deposition process at OCP and/or to the formation of a Au–Ga alloy; the other one at −0.9 V is due to the bulk deposition of Ga. The XPS measurement reveals that there is an oxide layer on the top of the gallium electrodeposit due to exposure to air. In situ STM measurements show that the first layer of the Ga deposit consists of islands of 10–30 nm in width and several nanometers in height surprisingly the result of an electroless deposition at the OCP. If the electrode potential is further reduced the bulk deposition of Ga sets in.     

The dipeptide H-Aib-l-Ala-OH ligand in copper(II) chemistry: Variation of product identity as a function of pH

A systematic investigation of the influence of “pH” on the product identity from the Cu^II/H-Aib-l-Ala-OH (LH) reaction system is described, where H-Aib-l-Ala-OH is α-aminoisobutyryl-l-alanine. The pH variation has led to the synthesis of two discrete complexes, the structures of which have been determined by single-crystal X-ray crystallography. The “low pH” complex {[CuClL](H₂O)_2.5}_n (1) is a 3D coordination polymer, in which the dipeptide monoanion L⁻ behaves as a η¹:η¹:η¹:μ₂ ligand binding one Cu^II atom through its amino nitrogen and neutral peptide oxygen, and an adjacent Cu^II atom through one of its carboxylate oxygen. The “higher pH” complex {[Cu(H₋₁L)(EtOH)](EtOH)}_n (2) is a chain (1D) compound, in which the dipeptide dianion H₋₁L²⁻ uses its amino nitrogen, deprotonated peptide nitrogen and both carboxylate oxygens to bridge two metal centres.     

Adsorption of MCPA pesticide by MgAl-layered double hydroxides

In the present study, the adsorption characteristics of the herbicide MCPA (4-chloro-2-methylphenoxyacetic acid) on layered double hydroxides (LDHs) were evaluated under laboratory conditions with particular attention to the effect of layer charge, original interlayer anion and morphology. The final objective is the use of LDHs and modified LDH materials as recyclable adsorbents and heterogeneous catalysts for the treatment of contaminated waste waters.The anionic clays tested were [Mg_1−xAl_x(OH)₂]^x+[X_x/m^m−·nH₂O] materials. The MCPA adsorption capacity was determined from adsorption isotherms and a kinetic study. We looked at the influence of the pH, the Mg²⁺/Al³⁺ ratio, i.e. the anion exchange capacity, the nature of the intercalated anion X (CO₃²⁻, NO₃⁻, Cl⁻) and the morphology of the adsorbent on the extent of adsorption. The adsorption isotherms, described by Freundlich model, are of S-type with tendency to L-type for high MCPA equilibrium concentration. Furthermore, the adsorption capacity increases with the layer charge density. Hence, MCPA adsorption on LDHs occurs by anion exchange in two steps, an external exchange followed by an interlayer exchange, which explain these changes of type within the same isotherm. Besides, the adsorption capacity depends on the nature of the starting anions, following the affinity order (NO₃⁻<Cl⁻<CO₃²⁻) proposed by Miyata and increases with the specific surface area.     

Electrochemistry of thulium on inert electrodes and electrochemical formation of a Tm–Al alloy from molten chlorides

The electrochemical behaviour of TmCl₃ solutions was studied in the eutectic LiCl–KCl in the temperature range 673–823 K using inert and reactive electrodes, i.e. W and Al, respectively.On an inert electrode, Tm(III) ions are reduced to metallic thulium through two consecutive steps:

Tm(III) + 1e ↔ Tm(II) and Tm(II) + 2e ↔ Tm(0)

The electroreduction of Tm(III) to Tm(II) was found to be quasi-reversible. The intrinsic rate constant of charge transfer, k⁰, as well as of the charge transfer coefficient, α, have been calculated by simulation of the cyclic voltammograms and logarithmic analysis of the convoluted curves. Electrocrystallization of thulium plays an important role in the electrodeposition process, being the nucleation mode affected by temperature.The diffusion coefficients of Tm(III) and Tm(II) ions have been found to be equal. The validity of the Arrhenius law was verified by plotting the variation of the logarithm of the diffusion coefficients vs. 1/T.The electrode reactions of Tm(III) solutions at an Al electrode were also investigated. The results showed that for the extraction of thulium from molten chlorides, the use of a reactive electrode made of aluminium leading to Al–Tm alloys seems to be a pertinent route.Potentiometric titrations of Tm(III) solutions with oxide donors, using a ytria stabilized zirconia electrode “YSZE” as a pO²⁻ indicator electrode, have shown the formation of thulium oxychloride and thulium oxide and their corresponding solubility products have been determined at 723 K (pk_s(TmOCl) = 8.0 ± 0.3 pk_s(Tm₂O₃) = 18.8 ± 0.7).     

Electrochemical investigations of antioxidant interactions with radical anion and dianion of 1,3-dinitrobenzene

Interactions of five antioxidants (AO), quercetin (Q), morin (M), rutin (R), ascorbic acid (AA) and β-carotene (β-C) with anion radical and dianion of 1,3-dinitrobenzene (1,3-DNB) in two aprotic solvents – dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) – have been studied by cyclic voltammetry using glassy carbon electrode. Electrochemical parameters – peak potential (E_p), half-wave potential (E_1/2), and peak current (i_p) – for the reduction of 1,3-DNB before and after the addition of various concentrations of antioxidants, were evaluated. A gradual decrease in the oxidation peak current and finally irreversibility in 1,3-DNB radical anion and dianion systems upon the addition of antioxidant, reveals their interactions. The homogeneous bi-molecular rate constant (k₂) was determined from electrochemical data. In comparison to all other antioxidants used, enhanced homogeneous second order rate constant for the interaction of morin with 1,3-DNB anion radical and dianion, was observed. This aspect is attributable to protonation initiated by hydrogen bonding and greater acidic nature of morin.     

Application of silica gel as an effective modifier for the voltammetric determination of dopamine in the presence of ascorbic acid and uric acid

Amorphous silica gel modified carbon paste electrode (CPE) offers substantial improvements in voltammetric sensitivity and selectivity towards determination of dopamine (DA). Cyclic voltammetry of Fe(CN)₆^3−/4− as a negatively charged probe revealed that the surface of the silica gel modified carbon paste electrode had a high density of negative charge at pH 8.0. Therefore, the modified electrode adsorbed DA (pK_a = 8.9) and enhanced its voltammetric response while repulsed ascorbic acid (AA) (pK_a = 4.2) and uric acid (UA) (pK_a = 5.4) and inhibited their interfering effects. The influence of various experimental parameters including percent of silica gel in the CPE, pH of solution, and accumulation time and potentials, on the voltammetric response of DA was investigated. At the optimum conditions, the analytical curve was linear for dopamine concentrations from 2.0 × 10⁻⁷ to 1.0 × 10⁻⁶ mol L⁻¹ and 2.0 × 10⁻⁶ to 1.5 × 10⁻⁴ mol L⁻¹ with a detection limit (3σ) of 4.8 × 10⁻⁸ mol L⁻¹. The prepared electrode was used for determination of DA spiked into DA injection and human serum samples, and very good recovery results were obtained over a wide concentration range of DA.     

Thermodynamic studies of phosphate adsorption on Pt(1 1 1) electrode surfaces in perchloric acid solutions

The thermodynamics of the so-called perfectly polarizable electrode was employed to analyze the total charge densities for a nearly defect-free Pt(1 1 1) electrode in a series of NaH₂PO₄ solutions with an excess of inert electrolyte (0.1 M HClO₄) at constant ionic strength and pH. Thermodynamic analysis using both electrode potential and charge density as independent electrical variables is described. The Gibbs excess, Gibbs energy of adsorption and charge numbers both at constant electrode potential and constant chemical potential for anion adsorption at the Pt(1 1 1) surface have been determined. The calculated electrosorption valencies and charge numbers at constant chemical potential are close to two electrons per adsorbed anion, suggesting that in the absence of co-adsorbed species, HPO₄²⁻ is the predominant adsorbed species. The maximum Gibbs excess of adsorbed hydrogenphosphate attains a value of ≈3.2 × 10¹⁴ ions cm⁻² which corresponds to a coverage of ≈0.22 ML.     

Carbon nanotube-supported Pd–ZnO catalyst for hydrogenation of CO2 to methanol

A type of Pd–ZnO catalysts supported on multi-walled carbon nanotubes (MWCNTs) were developed, with excellent performance for CO₂ hydrogenation to methanol. Under reaction conditions of 3.0 MPa and 523 K, the observed turnover-frequency of CO₂ hydrogenation reached 1.15 × 10⁻² s⁻¹ over the 16%Pd_0.1Zn₁/CNTs(h-type). This value was 1.17 and 1.18 times that (0.98 × 10⁻² and 0.97 × 10⁻² s⁻¹) of the 35%Pd_0.1Zn₁/AC and 20%Pd_0.1Zn₁/γ-Al₂O₃ catalysts with the respective optimal Pd_0.1Zn₁-loading. Using the MWCNTs in place of AC or γ-Al₂O₃ as the catalyst support displayed little change in the apparent activation energy for the CO₂ hydrogenation, but led to an increase of surface concentration of the Pd⁰-species in the form of PdZn alloys, a kind of catalytically active Pd⁰-species closely associated with the methanol generation. On the other hand, the MWCNT-supported Pd–ZnO catalyst could reversibly adsorb a greater amount of hydrogen at temperatures ranging from room temperature to 623 K. This unique feature would help to generate a micro-environment with higher concentration of active H-adspecies at the surface of the functioning catalyst, thus increasing the rate of surface hydrogenation reactions. In comparison with the “Parallel-type (p-type)” MWCNTs, the “Herringbone-type (h-type)” MWCNTs possess more active surface (with more dangling bonds), and thus, higher capacity for adsorbing H₂, which make their promoting action more remarkable.     

Direct electron transfer of hemoglobin in a CdS nanorods and Nafion composite film on carbon ionic liquid electrode

In this paper the direct electron transfer of hemoglobin (Hb) was carefully investigated by using a room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) modified carbon paste electrode (CILE) as the basal working electrode. Hb was immobilized on the surface of CILE with the nanocomposite film composed of Nafion and CdS nanorods by a step-by-step method. UV–vis and FT-IR spectra showed that Hb in the composite film remained its native structure. The direct electrochemical behaviors of Hb in the composite film were further studied in a pH 7.0 phosphate buffer solution (PBS). A pair of well-defined and quasi-reversible cyclic voltammetric peaks of Hb was obtained with the formal potential (E⁰′) at −0.295 V (vs. SCE), which was the characteristic of heme Fe(III)/Fe(II) redox couples. The direct electrochemistry of Hb was achieved on the modified electrode and the apparent heterogeneous electron transfer rate constant (k_s) was calculated to be 0.291 s⁻¹. The formal potentials of Hb Fe(III)/Fe(II) couple shifted negatively with the increase of buffer pH and a slope value of −45.1 mV/pH was got, which indicated that one electron transfer accompanied with one proton transportation. The fabricated Hb sensor showed good electrocatalytic manner to the reduction of trichloroacetic acid (TCA).     

Magnetic properties of CNX whiskers

Carbon–nitrogen whiskers have been prepared by pyrolysis of 1,2-diaminopropane at 950 °C or of allylamine at 900 °C followed by quenching. They are scrolls of carbon film typically 250 nm thick and up to 1 mm long with about five layers in a structure like a “cigare russe” or “brandy snap”, about 50 μm in diameter. Approximately 8 wt% of nitrogen is incorporated into the carbon films, which are practically amorphous, exhibiting a broad diffraction peak at d = 0.34 nm. The whiskers are on the border of metallic conductivity with a resistivity of about 10⁻⁶ Ωm, and they may show either a positive or a negative temperature coefficient of resistance. The pyrolysis produces either whiskers, soot or both. Magnetization measurements of the whiskers made from 1,2-diaminopropane reveal a large diamagnetic susceptibility of χ = −170 × 10⁻⁹ m³  kg⁻¹ and a small ferromagnetic component of unknown origin with σ_S of up to 0.2 A m² kg⁻¹, whereas the soot shows a purely diamagnetic signal, with χ ≈ −40 × 10⁻⁹ m³ kg⁻¹.     

Proton diffusion in γ-manganese dioxide

Deconvolution of the electrolytic manganese dioxide (EMD) discharge curve has indicated the presence of a number of energetically different reduction processes. This has been used to determine the contribution of each reduction process to the total discharge. Using step potential electrochemical spectroscopy (SPECS), the i-t data were modelled as the sum of the discharge of the individual reduction processes. From this, A√ D for each reduction process as a function of degree of discharge was determined. The maximum A√ D values for each process ranged from 2.3×10⁻² to 4.0×10⁻⁴ cm³ s^−1/2 g⁻¹ values are consistent with previously reported values for A√ D, although in this case we have determined values for the entire compositional range.     

Sorption of humic acid on zeolitic tuff: a preliminary investigation

This work involves a study of the interaction of humic acid (HA) with zeolitic (phillipsite+chabazite) Neapolitan yellow tuff (NYT). HA sorption isotherms were carried out on untreated as well as on Li⁺-, Na⁺-, K⁺-, NH₄⁺-, Ca²⁺-, Mg²⁺-, or Ba²⁺-enriched samples. Except for the Li-enriched sample, Langmuir sorption curves fitted the experimental data, allowing the calculation of the maximum HA sorbable amount, Q_max, and the affinity constant between the sorbate and the sorbent, k. The Q_max for the untreated sample was 8512±265 mg kg⁻¹, with k=10.8±1.4 l kg⁻¹. The experimental amounts of HA taken up by the Li-enriched sample were very small (183 to 2322 mg kg⁻¹) and too scattered to be consistently fitted by any significant equation. For other cation enriched-samples, the HA-Q_max amounts ranged from 6583±205 mg kg⁻¹ for the K-treated tuff to 22 029±1065 mg kg⁻¹ for the Mg-treated tuff, whereas the k values ranged from 8.0±1.7 l kg⁻¹ for the Na-treated tuff to 81.4±17.5 l kg⁻¹ for the Ba-treated tuff. The tuff samples enriched by divalent cations took up HA in amounts larger than those observed for the untreated sample; the opposite was true for the monovalent cation-enriched samples. The HA sorption curves on monovalent cation-enriched tuff were scarcely different, within experimental variance, from those observed for the untreated sample. On the contrary, both the Q_max and the k values calculated for the HA sorption on the divalent cation-enriched samples were widely and significantly larger than those of the untreated sample, with the highest Q_max for Mg- and Ca-enriched sample, and the highest k value for the Ba-enriched one. The results demonstrate that enrichment by divalent cations enhances the ability of Neapolitan yellow tuff to take up humic acid, whereas enrichment by monovalent cations reduces it; the results also show that humic acid sorption on tuff must be regarded as a complex phenomenon, occurring as a compromise between the ability of the cations to form stable bridges with the organic matter, and, on the other hand, their specific selective sorption by the tuff.     

Spatial variability of transport parameters in the Boom Clay

Several transport parameters (as hydraulic conductivity K, apparent diffusion coefficient D_p and diffusion accessible porosity η of HTO and iodide) have been intensively measured in the laboratory on high-quality cores taken at the Mol-1 borehole of the Mol site, in Belgium. The borehole was cored in 1997 from about 145 to 325 m depth, including the whole thickness of the Boom Formation, a Tertiary clay situated between 186 and 288 m depth (ground level), and part of the surrounding layers.The hydraulic conductivity measurements confirm the low permeability of the Boom Clay. An upper 90-m-thick clay layer within this formation can be considered as homogeneous with respect to the hydraulic conductivity. The vertical hydraulic conductivity K_v (i.e. K perpendicular to the bedding) is in the order of magnitude of 10⁻¹² m s⁻¹ and the average is 2.3×10⁻¹² m s⁻¹. This layer comprises from top to bottom the “Transition Zone”, the Putte Member, the Terhagen Member and the top of the Belsele-Waas Member of the Boom Formation. The 12 m at the base of the Formation, which corresponds to the lower part of the Belsele-Waas Member is characterised by larger K_v values (ranging between 10⁻¹¹ and 9×10⁻¹¹ m s⁻¹).The same thick clay layer can also be considered as homogeneous, regarding the values of the apparent diffusion coefficient and the diffusion accessible porosity η of tritiated water (HTO) and iodide. The average value of the diffusion accessible porosity is 0.37±0.03 for HTO and 0.16±0.02 for iodide. The apparent diffusion coefficient varies from 1.1×10⁻¹⁰ to 5.5×10⁻¹⁰ m² s⁻¹ for HTO and from 9.1×10⁻¹¹ to 5.2×10⁻¹⁰ m² s⁻¹ for iodide.     

Calibration of a kinetic model for wet air oxidation (WAO) of substituted phenols: Influence of experimental data on model prediction and practical identifiability

Calibration of kinetic models of wet air oxidation (WAO) is usually performed through minimisation algorithms with respect to total organic carbon (TOC) experimental data. However, the reliability of the estimated value of the kinetic parameters is frequently not reported. Moreover, the influence of data quantity/quality in the kinetic parameters identifiability is not properly assessed. The objective of this study is to compare the calibration goodness of a proposed kinetic model when using one set of data (total effluent TOC [TOC_eff]) or two sets of independent experimental measurements (total effluent TOC [TOC_eff] and residual TOC of target pollutant [TOC_[A]]). The systematic comparison was made using identifiability analysis with contour plots of both objective functions and the confidence intervals were calculated through the Fisher information matrix (FIM). The experimental data used in this study comes from a previous one, where WAO was investigated as a suitable precursor for the biological treatment of industrial wastewater containing high concentrations of o-cresol or 2-chlorophenol [M.E. Suárez-Ojeda, J. Carrera, I.S. Metcalfe, J. Font, Wet air oxidation (WAO) as a precursor to biological treatment of substituted phenols: refractory nature of the WAO intermediates, Chem. Eng. J. 144 (2008) 205–212.]. The results show that the model correctly fitted the experimental [TOC_eff] in all cases with less than 6% as averaged relative deviation, either using one set of data ([TOC_eff]) or two sets of independent experimental measures ([TOC_eff] and [TOC_[A]]) in the objective function. However, when using only [TOC_eff], the model was not capable of fitting the proportion between [TOC_[A]] and intermediates TOC. The obtained E_ACT for the calibration made with [TOC_eff] and [TOC_[A]] were 71 ± 20 kJ mol⁻¹ (R² = 0.92) and 47 ± 9 kJ mol⁻¹ (R² = 0.96) for o-cresol and 2-chlorophenol, respectively. However, when using just [TOC_eff], the obtained E_ACT values were not in the range of the values reported in the literature and had smaller regression coefficients. Moreover, the calibration with just [TOC_eff] presented a high correlation between the obtained rate constants, whereas the calibration with [TOC_eff] and [TOC_[A]] was statistically more reliable. As example, the D-criterion values are three to six times larger for the calibration made with ([TOC_eff] and [TOC_[A]] than for the calibration made only with [TOC_eff], in the framework of OED/PE criteria, this is related to minimisation of the geometric mean of the identification errors.     

Biological COD reduction and inorganic suspended solids accumulation in a pilot-scale membrane bioreactor for traditional Chinese medicine wastewater treatment

A pilot-scale test was conducted in a membrane bioreactor (MBR) for 452 days to treat high-strength traditional Chinese medicine (TCM) wastewater from two-phase anaerobic digest effluent. This study focuses on the chemical oxygen demand (COD) reduction and inorganic suspended solid (ISS) accumulation. The wastewater was high in COD, varying daily between 259 and 12,776 mg L⁻¹. Almost all the COD was removed by the MBR system, leaving a COD of <50 mg L⁻¹ in the MBR effluent. This indicated a great potential of the MBR in TCM wastewater reuse. ISS produced in the bioreactor by metabolism of microorganism increased from 265 to 4912 g h⁻¹, which showed that there were large numbers of ISS accumulation in the bioreactor. Two models, built on the material balances of COD and ISS, were developed for the simulation of MBR system performance in the biodegradation of TCM wastewater. Consequently, the kinetic constants including the maximum substrate specific biodegradation rate (V_max), the half-saturation coefficient (K_s) and the inorganic suspended solids growth rate (k) were calculated as V_max, 3.64, 3.82, 4.39 d⁻¹, K_s, 56.4, 225, 394 mg L⁻¹ and k, 265, 888, 4912 mg L⁻¹ d⁻¹ using the operational data at different hydraulic retention times (HRTs). The models well fitted the pilot-scale experimental data, and were able to simulate the COD reduction and ISS accumulation.     

Nickel inhibition of calcium precipitation by ureolytic mixed microorganisms under batch conditions

The respirometric assessment of the inhibitory impact of Ni(II) on substrate utilization and microbial carbonate precipitation (MCP) by ureolytic mixed microorganisms was investigated with a glucose containing mineral medium under batch conditions over an incubation period of 134 h. The IC₂₅ was determined as 224 mg Ni(II) L⁻¹ from the BOD values of samples. The interpretation of kinetic data showed that the substrate removal rate fitted a zero-order at the beginning of the incubation period and first-order during the last period, for a range of Ni(II) concentrations between 0 and 512 mg L⁻¹. Increasing Ni(II) concentrations from 0 to 512 mg L⁻¹ reduced the substrate degradation rate constant from 10.8 to 5.3 mg L⁻¹ h⁻¹ for zero-order rate constant (k₀), and from 0.015 to 0.002 h⁻¹ for first-order rate constant (k₁). The zero- and first-order reaction rates during incubation period were equalized to the reaction rate of the Monod equation in order to determine the kinetic constants, half saturation concentration (K_S) and maximum substrate removal rate (R_max). BOD removal rate was inhibited accordingly to mixed inhibition model with increasing Ni(II) concentrations during the calcification process. Also, the inhibition of calcium precipitation was observed at a higher Ni(II) concentration because of inhibition of ammonium production in these samples.