Application of activated M/ZnO (M = Mn,Co, Ni,Cu, Ag) in photocatalytic degradation of diazo textile coloring dye

Activated ZnO powder has been prepared by procedures involving first its dissolution in nitric acid, then simultaneous treatment by adding NH₄OH and CO₂ bubbling leading to precipitation as Zn(OH)CO₃ (ZH) and further thermal decomposition of ZH at 400 °C. The gas evolution leads to formation of pores and increase in the specific surface area. Chemically activated M/ZnO powders doped with Mn, Co, Ni, Cu, and Ag have been obtained by the impregnation method. The samples have been characterized by ultraviolet-visible (UV-Vis) spectroscopy, diffuse reflectance (DR) UV-Vis, X-ray diffraction (XRD), single point Brunauer–Emmet–Teller (BET), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) methods. The experiments have shown that metal-doped activated ZnO powders possess higher photocatalytic activities in oxidative discoloration of model contaminant textile coloring dye Reactive Black 5 in slurry reactor compared to that of the pure ZnO. The XRD and XPS data have shown the presence of defects, nonstoichiometricity implying the formation of solid solutions. Copper-doped (1.5 wt%) activated ZnO (Cu²⁺ replaces Zn²⁺) is outstanding in its photocatalytic performance in discoloration of the dye due to the higher specific surface area and improved charge carrier separation.     

Multi-component adsorption of copper,nickel and zinc from aqueous solutions onto activated carbon prepared from date stones

The removal of Cu²⁺, Ni²⁺, and Zn²⁺ ions from their multi-component aqueous mixture by sorption on activated carbon prepared from date stones was investigated. In the batch tests, experimental parameters were studied, including solution pH, contact time, initial metal ions concentration, and temperature. Adsorption efficiency of the heavy metals was pH-dependent and the maximum adsorption was found to occur at around 5.5 for Cu, Zn, and Ni. The maximum sorption capacities calculated by applying the Langmuir isotherm were 18.68 mg/g for Cu, 16.12 mg/g for Ni, and 12.19 mg/g for Zn. The competitive adsorption studies showed that the adsorption affinity order of the three heavy metals was Cu²⁺?>?Ni²⁺?>?Zn²⁺. The test results using real wastewater indicated that the prepared activated carbon could be used as a cheap adsorbent for the removal of heavy metals in aqueous solutions.     

Ni-Co bimetallic catalysts on coconut shell activated carbon prepared using solid-phase method for highly efficient dry reforming of methane

Ni-Co bimetallic catalysts supported on coconut shell activated carbon are synthesized using solid-phase method and investigated for dry reforming of methane, to explore the impact of Ni:Co ratio on the catalyst activity and stability. The catalyst performances are evaluated under the temperature varying from 600 to 900 °C and gas hourly space velocity (GHSV) of 7200 mL/h·g-cat. The characterization results show that metal nanoparticles are produced on the support, and the bimetallic catalyst with an explicit Ni:Co ratio (2:1) is the most beneficial for metal particle dispersion and acquires the minimum particle size of 4.41 nm. The bimetallic catalysts with an explicit Ni:Co ratio of 1:2 and 1:1 exhibit a synergistic effect towards the conversions of CH₄ and CO₂, respectively. The experimental results reveal that the highest CH₄ and CO₂ conversions rise to 94.0% and 97.5% within 12 h at 900 °C on average, respectively, assisted with the two bimetallic catalysts. The intensity of disordered carbon and thermal stability are enhanced with the extension of reforming process, contributing to a long-term catalytic stability. Besides, no obvious carbon deposition is detected, leading to a highly catalytic stability for the bimetallic catalysts.

     

Atmospheric corrosion effects of HNO3—Comparison of laboratory-exposed copper,zinc and carbon steel

The influence of nitric acid (HNO₃) on the atmospheric corrosion of copper, zinc and carbon steel was investigated in laboratory exposures at 65% relative humidity (RH), 25 °C and 0.03 cm s⁻¹ air velocity. The deposition velocity (V_d) of HNO₃ on the specimens, the corrosion rates and corrosion products were determined by gravimetry, ion chromatography, X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) microspectroscopy. Comparisons were also made with literature data on the corrosion effects of sulfur dioxide (SO₂), nitrogen dioxide (NO₂) and ozone (O₃).At 65% RH, the V_d of HNO₃ on all metals was at least 70% of that of an ideal absorbent, i.e., an impregnated filter with perfect absorption for HNO₃. The V_d of HNO₃ was much higher than that of SO₂, NO₂ or O₃, which is mainly attributed to the relatively high sticking coefficient, high solubility and high reactivity of HNO₃ compared to the other gases. During identical exposures to HNO₃, the corrosion rate of carbon steel was nearly three times higher than that of copper or zinc. However, when comparing the corrosion effects induced by HNO₃ with those induced by SO₂ alone or in combination with either NO₂ or O₃, HNO₃ turned out to be far more aggressive than SO₂. Relative to SO₂, zinc is the metal most sensitive to HNO₃, followed by copper and with carbon steel least sensitive to HNO₃.     

Ozone Injection into an Activated Carbon Bed to Remove Hydrogen Sulfide in the Presence of Concurrent Substances

ABSTRACT

Adsorption using activated carbon is one of the most reliable techniques for preventing odor by substances such as H₂S. Concurrent substances in effluent gas often reduce the removal capacity of activated carbon for H₂S. As a means of restoring capacity under such conditions, ozone injection into an activated carbon column was examined. When activated carbon was saturated with substances such as toluene, ethanol, n-butanol, or iso-butanol, its capacity to remove H₂S decreased in proportion to the amount of the saturating substance. Under such conditions, ozone injection greatly increased capacity. Toluene, which is not easily decomposed by ozone, was displaced by ozone and by oxidized products of H₂S. Ethanol, which is adsorbed in small amounts by activated carbon and easily decomposed by ozone, was removed by ozone injection. Butanols, which are also decomposed by ozone and adsorbed in large quantities by activated carbon, showed intermediate behavior between that of toluene and ethanol.     

Removal of bisphenol A and some heavy metal ions by polydivinylbenzene magnetic latex particles

In this study, magnetic polydivinylbenzene latex particles MP_DVB with a core-shell structure were tested for the removal of bisphenol A (BPA), copper Cu(II), lead Pb(II), and zinc Zn(II) from aqueous solutions by a batch-adsorption technique. The effect of different parameters, such as initial concentration of pollutant, contact time, adsorbent dose, and initial pH solution on the adsorption of the different adsorbates considered was investigated. The adsorption of BPA, Cu(II), Pb(II), and Zn(II) was found to be fast, and the equilibrium was achieved within 30 min. The pH 5–5.5 was found to be the most suitable pH for metal removal. The presence of electrolytes and their increasing concentration reduced the metal adsorption capacity of the adsorbent. Whereas, the optimal pH for BPA adsorption was found 7, both hydrogen bonds and π–π interaction were thought responsible for the adsorption of BPA on MP_DVB. The adsorption kinetics of BPA, Cu(II), Pb(II), and Zn(II) were found to follow a pseudo-second-order kinetic model. Equilibrium data for BPA, Cu(II), Pb(II), and Zn(II) adsorption were fitted well by the Langmuir isotherm model. Furthermore, the desorption and regeneration studies have proven that MP_DVB can be employed repeatedly without impacting its adsorption capacity.     

Pre-concentration and separation of heavy metal ions by chemically modified waste paper gel

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II)  Fe(III) > Pb(II) > Ni(II)  Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.     

Efficient abatement of an iodinated X-ray contrast media iohexol by Co(II) or Cu(II) activated sulfite autoxidation process

Efficient abatement of an iodinated X-ray contrast media iohexol by an emerging sulfite autoxidation advanced oxidation process is demonstrated, which is based on transition metal ion–catalyzed autoxidation of sulfite to form active oxidizing species. The efficacy of the combination of sulfite and transition metal ions (Ag(I), Mn(II), Co(II), Fe(II), Cu(II), Fe(III), or Ce(III)) was tested for iohexol abatement. Co(II) and Cu(II) are proven to show more pronounced catalytic activity than other metals at pH 8.0. According to the quenching studies, sulfate radical (SO₄^??) is identified to be the primary species for oxidation of iohexol. Increasing dosages of metal ion or sulfite and higher pH values are favorable for iohexol abatement. Inhibition of iohexol abatement is observed in the absence of dissolved oxygen, which is vital for the production of SO₅^?? and subsequent formation of SO₄^??. Overall, activation of sulfite to produce reactive radicals with extremely low Co(II) or Cu(II) concentrations (in the range of μg L^?1) in circumneutral conditions is confirmed, which offers a potential SO₄^??-based advanced oxidation process in treatment of aquatic organic contaminants.

     

Probing the distribution and contamination levels of 10 trace metal/metalloids in soils near a Pb/Zn smelter in Middle China

The horizontal and vertical distribution patterns and contamination status of ten trace metal/metalloids (Ag, Bi, Co, Cr, Ge, In, Ni, Sb, Sn, Tl) in soils around one of the largest Chinese Pb–Zn smelter in Zhuzhou City, Central China, were revealed. Different soil samples were collected from 11 areas, including ten agricultural areas and one city park area, with a total of 83 surface soil samples and six soil cores obtained. Trace metal/metalloids were determined by inductively coupled plasma–mass spectrometry after digestion by an acid mixture of HF and HNO₃. The results showed that Ag, Bi, In, Sb, Sn, and Tl contents decreased both with the distance to the Pb–Zn smelter as well as the soil depth, hinting that these elements were mainly originated from the Pb–Zn smelting operations and were introduced into soils through atmospheric deposition. Soil Ge was influenced by the smelter at a less extent, while the distributions of Co, Cr, and Ni were roughly even among most sampling sites and soil depths, suggesting that they were primarily derived from natural sources. The contamination status, as revealed by the geo-accumulation index (I _geo), indicated that In and Ag were the most enriched elements, followed by Sb, Bi, and Sn. In general, Cr, Tl, Co, Ni, and Ge were of an uncontaminated status.     

Evaluation of an approach for the characterization of reactive and available pools of twenty potentially toxic elements in soils: Part I – The role of key soil properties in the variation of contaminants’ reactivity

Harmful effects of potentially toxic elements (PTE’s) in soils relate to their geochemically reactive fraction. To assess the degree of the reactivity, specific extractions or models are needed. Here we applied a 0.43 M HNO₃ chemical extraction to assess reactive pools of a broad range of PTE’s in 136 contaminated and non-contaminated soils. Furthermore we derived Freundlich-type models based on commonly available soil properties (pH, organic carbon and clay) as well as extended models that used other properties such as amorphous Al and Fe oxides and evaluated their possible use in risk assessment.The approach allowed to predict the reactivity of As, Hg, Co, U, Ba, Se, Sb, Mo, Li, Be (r²: 0.55–0.90) elements not previously included in such studies, as well as that of Cd, Zn, Cu, Pb, Ni and Cr (r²: 0.73–0.90). The inclusion of pH, organic carbon and clay improved the performance of all models except for Be and Mo, although the role of clay is not completely clear and requires further investigation. The ability of amorphous metal oxides to affect the reactivity of As, Hg, Cu, Ni, Cr, Sb, Mo and Li was expressed by the models in agreement with known geochemical processes leading to the retention of PTE’s by the solid matrix. Hence, such approach can be a useful tool to account for regional differences in soil properties during the identification of risk areas and constitute a significantly more powerful tool than the analysis of total pools of PTE’s in soils.     

Evaluation of heavy metal concentrations of edible wild-grown mushrooms from China

ABSTRACT

The heavy metal contents (Co, Cu, Fe, Mn, Ni, and Zn) of eight species of wild edible mushrooms from China were determined. The analyses were performed using inductively coupled plasma atomic emission spectrophotometry after microwave digestion. The contents of Co, Cu, Fe, Mn, Ni, and Zn in caps of mushroom samples were 0.7–7.2, 16.2–70.4, 371–1315, 12.5–29.8, 7.1–58.5, and 77.8–187.4 mg kg^?1 dry matter (dm), respectively, while considerable differences were found to be 1.8–25.9, 9.8–36.3, 288–6762, 13.3–103.9, 5.9–78.7, and 38.7–118 mg kg^?1 dm for stipes. The results indicated that higher levels of Co, Fe, and Ni were found in the mushrooms samples analyzed. Zinc and manganese levels were similar to previous reports, whereas Cu was lower than literature values. Correlation analysis suggested that significant correlations were found between the minerals determined and the greatest amount of contamination is associated with Co, Mn, Ni, and Fe. The results of this study indicate that heavy metal contents in mushroom species are mainly related to the mineral resources of sampling sites.     

Agricultural solid waste for sorption of metal ions: part I—characterization and use of lettuce roots and sugarcane bagasse for Cu(II), Fe(II), Zn(II), and Mn(II) sorption from aqueous medium

Sugarcane bagasse and hydroponic lettuce roots were used as biosorbents for Cu(II), Fe(II), Zn(II), and Mn(II) removal from monoelemental solutions in aqueous medium, at pH 5.5, using batch procedures. These biomasses were studied in natura (lettuce roots, NLR, and sugarcane bagasse, NSB) and modified with HNO₃ (lettuce roots, MLR, and sugarcane bagasse, MSB). Langmuir, Freundlich, and Dubinin-Radushkevich non-linear isotherm models were used to evaluate the data from the metal ion adsorption assessment. The maximum adsorption capacities (q_max) in monoelemental solution, calculated using the Langmuir isothermal model for Cu(II), Fe(II), Zn(II), and Mn(II), were respectively 24.61, 2.64, 23.04, and 5.92 mg/g for NLR; 2.29, 16.89, 1.97, and 2.88 mg/g for MLR; 0.81, 0.06, 0.83, and 0.46 mg/g for NSB; and 1.35, 2.89, 20.76, and 1.56 mg/g for MSB. The Freundlich n parameter indicated that the adsorption process was favorable for Cu(II) uptake by NLR; Fe(II) retention by MLR and MSB; and Zn(II) sorption by NSB, MLR, and NSB and favorable for all biomasses in the accumulation of Mn(II). The Dubinin-Radushkevich isotherm was applied to estimate the energy (E) and type of adsorption process involved, which was found to be a physical one between analytes and adsorbents. Organic groups such as O–H, C–O–C, CH, and C=O were found in the characterization of the biomass by FTIR. In the determination of the biomass surface charges by using blue methylene and red amaranth dyes, there was a predominance of negative charges.     

Removal of Ni(II) and Cu(II) ions using native and acid treated Ni-hyperaccumulator plant Alyssum discolor from Turkish serpentine soil

Alyssum discolor biomass was collected from serpentine soil and was used for removal of metal ions. The plant species grown on serpentine soils are known to be rich with metals ions and thus have more capability for accumulating heavy metals. Native and acid-treated biomass of A. discolor (A. discolor) were utilized for the removal of Ni(II) and Cu(II) ions from aqueous solutions. The effects of contact time, initial concentration, and pH on the biosorption of Ni(II) and Cu(II) ions were investigated. Biosorption equilibrium was established in about 60 min. The surface properties of the biomass preparations were varied with pH, and the maximum amounts of Ni(II) and Cu(II) ions on both A. discolor biomass preparations were adsorbed at pH 5.0. The maximum biosorption capacities of the native, and acid-treated biomass preparations for Ni(II) were 13.1 and 34.7 mg g⁻¹ and for Cu(II) 6.15 and 17.8 mg g⁻¹ dry biomass, respectively. The biosorption of Ni(II) and Cu(II) ions from single and binary component systems can be successfully described by Langmuir and Freundlich isotherms. When the heavy metal ions were in competition, the amounts of biosorbed metal ions on the acid treated plant biomass were found to be 0.542 mmol g⁻¹ for Ni(II) and 0.162 mmol g⁻¹ for Cu(II), the A. discolor biomass was significantly selective for Ni(II) ions. The information gained from these studies was expected to indicate whether the native, and acid-treated forms can have the potential to be used for the removal and recovery of Ni(II) ions from wastewaters.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

In situ measurements of HNO3, NOy,NO, and O3 in the lower stratosphere and upper troposphere

In situ measurements of nitric acid (HNO₃), reactive nitrogen (NO_y), nitric oxide (NO), and ozone (O₃) made in the upper troposphere (UT) and lower stratosphere (LS) between 29° and 33°N latitudes during September 1999 are used to examine NO_y partitioning and correlations between the measured species in these regions. The fast-response (1 s) HNO₃ measurements are acquired with a new autonomous CIMS instrument. In the LS, HNO₃ accounts for the majority of NO_y, and the sum of HNO₃ and NO_x accounts for approximately 90% of NO_y. In the UT, the sum of HNO₃ and NO_x varies between 40% and 100% of NO_y. Both HNO₃ and NO_y are strongly positively correlated with O₃, with larger correlation slopes in the UT than in the LS. In the UT at low values of the quantity (NO_y–NO_x–HNO₃), it is uncorrelated with O₃, while at higher values, a positive correlation with O₃ is found. Of these two air mass types, those with higher (NO_y–NO_x–HNO₃) mixing ratios are likely associated with the presence of peroxyacetyl nitrate (PAN) that is produced by NO_x-hydrocarbon chemistry.     

Adsorption kinetics and modeling of H2S by treated waste oil fly ash

Waste oil fly ash (OFA) collected from disposal of power generation plants was treated by physicochemical activation technique to improve the surface properties of OFA. This synthesized material was further used for potential hydrogen sulfide (H₂S) adsorption from synthetic natural gas. The raw OFA was basically modified with a mixture of acids (20% nitric acid [HNO₃] and 80% phosphoric acid [H₃PO₄]), and it was further treated with 2 M potassium hydroxide (KOH) to enhance the surface affinity as well as surface area of synthesized activated carbon. Correspondingly, it enhanced the adsorption of H₂S. Crystallinity, surface morphology, and pore volume distribution of prepared activated carbon were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analyses. Fourier transform infrared (FTIR) study was also performed to identify the functional groups during different synthesis stages of modified activated carbon. The Langmuir, Freundlich, Sips, and dual-site Langmuir (DSL) models were used to study the kinetic and breakthrough behavior of H₂S adsorption over alkali-modified activated carbon. Modeling results of isotherms indicated that OFA has dual sites with high and low affinity for H₂S adsorption. The Clark model, Thomas model, and Yoon-Nelson model were used to examine the effects of flow rate and inlet concentration on the adsorption of H₂S. Maximum uptake capacity of 8.5 mg/g was achieved at 100 ppm inlet concentration and flow rate of 0.2 L/min.

Implications: Utilization of worthless oil fly ash from power plant is important not only for cleaning the environment but also for solid waste minimization. This research scope is to eradicate one pollutant by using another pollutant (waste ash) as a raw material. Chemical functionalization of synthesized activated carbon from oil fly ash would lead to attachment of functional groups of basic nature to attract the acidic H₂S. Such type of treatment can enhance the uptake capacity of sorbent several times.     

活性焦表面性质对CUO/AC脱硫性能的影响

分别以不同浓度的硝酸处理活性焦载体,采用硝酸铜溶液浸渍法制备CuO/AC催化剂,利用BET、FT-IR和XRD等方法对载体及催化剂进行表征.考察了不同浓度的硝酸处理对活性焦载体性质的影响,并对制得的催化剂的脱硫性能进行了比较.结果表明,活性焦经过硝酸处理后孔结构参数变化很小,而表面含氧酸性官能团的含量有了很大的提高,使...     

活性炭-臭氧体系处理含氰废水的作用机理

针对活性炭催化臭氧化降解低质量浓度含氰废水体系,研究了活性炭吸附、催化作用在催化臭氧化体系中的作用,提出了吸附-催化臭氧化协同作用机理。在活性炭-臭氧体系中,活性炭吸附CN-的能力很弱,活性炭在反应体系中主要起了吸附、催化臭氧的作用。活性炭-臭氧体系降解CN-的过程是臭氧直接氧化、活性炭吸附臭氧与活性炭催化臭氧产生.OH自由基间接氧化三者共同作用的结果。     

Agricultural solid waste for sorption of metal ions,part II: competitive assessment in multielemental solution and lake water

Sugarcane bagasse and hydroponic lettuce roots were used as biosorbents for the removal of Cu(II), Fe(II), Mn(II), and Zn(II) from multielemental solutions and lake water, in batch processes. These biomasses were studied in natura (lettuce roots, NLR, and sugarcane bagasse, NSB) and chemically modified with HNO₃ (lettuce roots, MLR, and sugarcane bagasse, MSB). The results showed higher adsorption efficiency for MSB and either NLR or MLR. The maximum adsorption capacities (q_max) in multielemental solution for Cu(II), Fe(II), Mn(II), and Zn(II) were 35.86, 31.42, 3.33, and 24.07 mg/g for NLR; 25.36, 27.95, 14.06, and 6.43 mg/g for MLR; 0.92, 3.94, 0.03, and 0.18 mg/g for NSB; and 54.11, 6.52, 16.7, and 1.26 mg/g for MSB, respectively. The kinetic studies with chemically modified biomasses indicated that sorption was achieved in the first 5 min and reached equilibrium around 30 min. Sorption of Cu(II), Fe(II), Mn(II), and Zn(II) in lake water by chemically modified biomasses was 24.31, 14.50, 8.03, and 8.21 mg/g by MLR, and 13.15, 10.50, 6.10, and 5.14 mg/g by MSB, respectively. These biosorbents are promising and low costs agricultural residues, and as for lettuce roots, these showed great potential even with no chemical modification.     

Adsorption of Cu2+ and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes

Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO₃ activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu²⁺ and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N₂ adsorption, CO₂ adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.