A review of the present methods used to remediate soil and water contaminated with organophosphate esters and developmental directions.

Organophosphate esters (OPEs) are widely used commercial additives, but their environmental persistence and toxicity raise serious concerns necessitating associated remediation strategies. Although there are various existing technologies for OPE removal, comprehensive screening for them is urgently needed to guide further research. This review provides a comprehensive overview of the techniques used to remove OPEs from soil and water, including their related influencing factors, removal mechanisms/degradation pathways, and practical applications. Based on an analysis of the latest literature, we concluded that (1) methods used to decontaminate OPEs include adsorption, hydrolysis, photolysis, advanced oxidation processes (AOPs), activated sludge processes, and microbial degradation; (2) factors such as the quantity/characteristics of the catalysts/additives, pH value, inorganic ion concentration, and natural organic matter (NOM) affect OPE removal; (3) primary degradation mechanisms involve oxidation induced by reactive oxygen species (ROS) (including •OH and SO4•-) and degradation pathways include hydrolysis, hydroxylation, oxidation, dechlorination, and dealkylation; (5) interference from the pH value, inorganic ion and the presence of NOM may limit complete mineralization during the treatment, impacting practical application of OPE removal techniques. This review provides guidance on existing and potential OPE removal methods, providing a theoretical basis and innovative ideas for developing more efficient and environmentally friendly techniques to treat OPEs in soil and water.

Metronidazole degradation mechanism by sono-photo-Fenton processes using a spinel ferrite cobalt on activated carbon catalyst.

A heterogeneous catalyst was prepared by anchoring spinel cobalt ferrite nanoparticles on porous activated carbon (SCF@AC). The catalyst was tested to activate hydrogen peroxide (HP) in the Fenton degradation of metronidazole (MTZ). SCF nanoparticles were produced through the co-precipitation of iron and cobalt metal salts in an alkaline condition. Elemental mapping, physico-chemical, morphological, structural, and magnetic properties of the as-fabricated catalyst were analyzed utilizing EDX mapping, FESEM-EDS, TEM, BET, XRD, and VSM techniques. The porous structure of AC enhanced the catalytic activity of SCF by a significant decrease in the agglomeration of SCF nanoparticles. The effectiveness of SCF@AC in Fenton degradation improved substantially when UV light and ultrasound (US) irradiations were induced, most likely due to the strong synergistic effect between the catalyst and these irradiation sources. The photo-Fenton system was more efficient than the Fenton, sono-, and sono-photo-Fenton processes eliminating both MTZ and TOC. It was found that AC not only dispersed SCF nanoparticles and improved the stability of the catalyst, but also provided a high adsorption capacity of MTZ, resulting in a faster degradation. After 60 min of the photo-Fenton reaction, the elimination efficiencies of MTZ (30 mg L-1) and TOC were 97 and 42.1% under optimum operational conditions (pH = 3.0, HP = 4.0 mM, SCF@AC = 0.3 g L-1, and UV = 6 W). SCF@AC showed excellent stability with low leaching of metal ions during the reaction. Radical and non-radical (O2•-, HO•, and 1O2 species), alongside adsorption and photocatalysis mechanisms, were responsible for MTZ decontamination over the SCF@AC/HP/UV system. A comprehensive study on the HP activation mechanism and MTZ degradation pathway was obtained through scavenging tests. The findings demonstrate that SCF@AC is an effective, reusable, and environmentally sustainable catalyst for advanced oxidation processes that can effectively remove organic pollutants from wastewater. This study offers valuable insights into the feasibility of employing SCF@AC catalysts in Fenton-based processes for the degradation of MTZ.

Effect of synthesis conditions on the porous texture of activated carbons obtained from Tara Rubber by FeCl3 activation.

This paper presents the results of an unique analysis of the influence of the mass ratio of activator FeCl3 to precursor and the temperature of the activation process on the formation of the porous structure of activated carbons obtained from Tara Rubber by FeCl3 activation. The study used the new numerical clustering based adsorption analysis method and the quenched solid density functional theory, taking into account, among other things, the heterogeneity of the analysed surface which is a new approach rarely used in the analysis of the porous structure of adsorbents. On the basis of the calculation results, it was concluded that the activated carbon with the most developed porous texture was obtained at a mass ratio (FeCl3:Tara Rubber) of 2, at an activation process temperature of 800 °C. This activated carbon is also characterised by the lowest degree of surface heterogeneity and at the same time, however, the widest range of micropores compared to activated carbons obtained at other mass ratios. The analyses carried out further demonstrated the valuable and complementary information obtained from the structure analysis methods and their high utility in practical applications, especially in the development of new industrial technologies for the production of adsorbents and the selection of optimal conditions for their production.

Spinel cobalt ferrite-based porous activated carbon in conjunction with UV light irradiation for boosting peroxymonosulfate oxidation of bisphenol A.

Developing heterogeneous catalysts with high performance for peroxymonosulfate (PMS) activation to decontaminate organic pollutants from wastewater is of prominent importance. In this study, spinel cobalt ferrite (CoFe2O4) materials were coated on the surface of powdered activated carbon (CoFe2O4@PAC) via the facile co-precipitation method. The high specific surface area of PAC was beneficial for the adsorption of both bisphenol A (BP-A) and PMS molecules. The CoFe2O4@PAC-mediated PMS activation process under UV light could effectively eliminate 99.4% of the BP-A within 60 min of reaction. A significant synergy effect was attained between CoFe2O4 and PAC towards PMS activation and subsequent elimination of BP-A. Comparative tests demonstrated that the heterogeneous CoFe2O4@PAC catalyst had a better degradation performance in comparison with its components and homogeneous catalysts (Fe, Co, and, Fe + Co ions). The formed by-products and intermediates during BP-A decontamination were evaluated using LC/MS analysis, and then a possible degradation pathway was proposed. Moreover, the prepared catalyst exhibited excellent performance in recyclability with slight leaching amounts of Co and Fe ions. A TOC conversion of 38% was obtained after five consecutive reaction cycles. It can be concluded that the PMS photo-activation process via the CoFe2O4@PAC catalyst can be utilized as an effective and promising method for the degradation of organic contaminants from polluted-water resources.

Structure sensitivity reaction of chloroform hydrodechlorination to light olefins using Pd catalysts supported on carbon nanotubes and carbon nanofibers.

The upgrading of wasted chloroform in hydrodechlorination for the production of olefins such as ethylene and propylene is studied by employing four catalysts (PdCl/CNT, PdCl/CNF, PdN/CNT, and PdN/CNF) prepared by different precursors (PdCl2 and Pd(NO3)2) supported on carbon nanotubes (CNT) or carbon nanofibers (CNF). TEM and EXAFS-XANES results confirm that Pd nanoparticle size increases in the order: PdCl/CNT < PdCl/CNF âˆ¼ PdN/CNT < PdN/CNF, descending the electron density of Pd nanoparticles in the same order. It illustrates that PdCl-based catalysts show donation of electrons from support to Pd nanoparticles, which is not observed in PdN-based catalysts. Moreover, this effect is more evident in CNT. The smallest and well-dispersed Pd nanoparticles (NPs) on PdCl/CNT with high electron density favor an excellent and stable activity and a remarkable selectivity to olefins. In contrast, the other three catalysts show lower selectivity to olefins and lower activities which suffer strong deactivation due to the formation of Pd carbides on their larger Pd nanoparticles with lower electron density, compared to PdCl/CNT.

Valorization of lignocellulosic biomass into sustainable materials for adsorption and photocatalytic applications in water and air remediation.

An exponential rise in global pollution and industrialization has led to significant economic and environmental problems due to the insufficient application of green technology for the chemical industry and energy production. Nowadays, the scientific and environmental/industrial communities push to apply new sustainable ways and/or materials for energy/environmental applications through the so-called circular (bio)economy. One of today's hottest topics is primarily valorizing available lignocellulosic biomass wastes into valuable materials for energy or environmentally related applications. This review aims to discuss, from both the chemistry and mechanistic points of view, the recent finding reported on the valorization of biomass wastes into valuable carbon materials. The sorption mechanisms using carbon materials prepared from biomass wastes by emphasizing the relationship between the synthesis route or/and surface modification and the retention performance were discussed towards the removal of organic and heavy metal pollutants from water or air (NOx, CO2, VOCs, SO2, and Hg0). Photocatalytic nanoparticle-coated biomass-based carbon materials have proved to be successful composites for water remediation. The review discusses and simplifies the most raised interfacial, photonic, and physical mechanisms that might take place on the surface of these composites under light irradiation. Finally, the review examines the economic benefits and circular bioeconomy and the challenges of transferring this technology to more comprehensive applications.

Direct growth of nano-worm-like Cu2S on copper mesh as a hierarchical 3D catalyst for Fenton-like degradation of an imidazolium room-temperature ionic liquid in water.

The increasing consumption of room-temperature ionic liquids (RTILs) inevitably releases RTILs into the water environment, posing serious threats to aquatic ecology due to the toxicities of RTILs. Thus, urgent needs are necessitated for developing useful processes for removing RTILs from water, and 1-butyl-3-methylimidazolium chloride (C4mimCl), the most common RTIL, would be the most representative RTIL for studying the removal of RTILs from water. As advanced oxidation processes with hydrogen peroxide (HP) are validated as useful approaches for eliminating emerging contaminants, developing advantageous heterogeneous catalysts for activating HP is the key to the successful degradation of C4mim. Herein, a hierarchical structure is fabricated by growing Cu2S on copper mesh (CSCM) utilizing CM as a Cu source. Compared to its precursor, CuO@CM, this CSCM exhibited tremendously higher catalytic activity for catalyzing HP to degrade C4mim efficiently because CSCM exhibits much more superior electrochemical properties and reactive sites, allowing CSCM to degrade C4mim rapidly. CSCM also exhibits a smaller Ea of C4mim elimination than all values in the literature. CSCM also shows a high capacity and stability for activating HP to degrade C4mim in the presence of NaCl and seawater. Besides, the mechanistic investigation of C4mim elimination by CSCM-activated HP has also been clarified and ascribed to OH and 1O2. The elimination route could also be examined and disclosed in detail through the quantum computational chemistry, confirming that CSCM is a useful catalyst for catalyzing HP to degrade RTILs.

Synthesis of zero-valent iron supported with graphite and plastic based carbon from recycling spent lithium ion batteries and its reaction mechanism with 4-chlorophenol in water.

Graphite and plastic recycled from spent lithium ion batteries were used to synthesize zero-valent iron/graphite (ZVI/G), zero-valent iron/plastic-based carbon (ZVI/P), and zero-valent iron/graphite and plastic-based carbon (ZVI/GP) with iron oxide through carbothermic reduction. The aim of preparing these catalysts is to improve the performance of ZVI in the removal of 4-chlorophenol (4-CP) in water through heterogeneous Fenton reactions. The structural and textural properties of materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption/desorption, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The synthesis procedure successfully disperses ZVI particles on the synthesized materials. The combination of graphite and plastic-based carbon in ZVI/GP resulted in the best 4-CP removal performance. The degradation data fitted pseudo-first-order kinetic well. The Increase in the ZVI/GP dosage and the hydrogen peroxide concentration enhanced the 4-CP removal due to the increase in the amount of Fe2+ ions and reactive sites. Acidic pH increased the 4-CP removal percentage due to the high H+ concentration. The increase in the temperature favored the •OH formation and facilitated the 4-CP removal. The reaction energy of ZVI/GP reaches 53.54 kJ mol-1, which is competitive among the iron catalysts reported in literatures, and showing the 4-CP removal is reaction-controlled process. This study shows a promising way of recycling graphite and plastic in spent LIBs to prepare ZVI materials for wastewater treatment with the advantages of improved conductivity by graphite and added functional groups by plastic based carbon.

Azaindole grafted titanium dioxide for the photodegradation of pharmaceuticals under solar irradiation.

The application of metal-free organic molecules grafted titanium dioxide (TiO2) as photocatalysts for the degradation of pharmaceuticals under solar light has been scarcely studied. Herein, a novel photocatalyst was synthesized anchoring a bipolar electron-donor and -acceptor molecule based on azaindole derivative (AZA4) onto TiO2 aiming to improve the photoactivity under simulated solar irradiation. The TiO2-azaindole (TiO2-AZA4) was fully characterized, confirming that AZA4 was successfully grafted onto TiO2 and improving the light absorption. The grafted TiO2 was applied in the photodegradation of acetaminophen in water, showing a significantly better photocatalytic performance compared to that of pure TiO2 under both solar and visible irradiations. AZA4 grafting leads to the TiO2 band gap narrowing and favors the charge separation, thus improving the TiO2 photoactivity. The photocatalytic performance of TiO2-AZA4 was evaluated using different conditions such as photocatalyst dose or initial pH of the solution, and the radical species involved in the process were investigated. The high activity of TiO2-AZA4 was confirmed in the photodegradation of a mixture of pharmaceuticals, namely acetaminophen, ibuprofen, and antipyrine, further demonstrating its stability and catalytic performance in a novel continuous flow test under simulated solar irradiation, thus finding a new strategy to design solar-light driven photocatalysts for the degradation of pollutants in water.

Removal of emerging pollutants in aqueous phase by heterogeneous Fenton and photo-Fenton with Fe2O3-TiO2-clay heterostructures.

Fe2O3-TiO2-clay heterostructures have been prepared using an organo-bentonite as support, which organophilic character favored the fixation of TiO2. Furthermore, Fe2O3 was successfully anchored by wet impregnation. The resulting materials are characterized by a disordered layered structure and a mesoporous texture. The heterostructures were employed as catalysts for the removal of two pharmaceuticals, acetaminophen (ACE) and antipyrine (ANT), by heterogeneous Fenton and photo-Fenton processes. ACE removal under different operation conditions was studied in detail to establish structure-performance relationships, being the TiO2 formation and the developed texture the main factors controlling the activity. ANT showed a higher refractory behavior in oxidation by Fenton. Among the technologies studied, heterogeneous photo-Fenton achieved the best catalytic performance and higher kinetic rate and mineralization degree. Iron leaching was very low, lower than 5% of the initial iron load in all cases. This work demonstrates the potential application of these heterostructures for the removal of emerging pollutants of different nature.

Comparison of the behavior of ZVI/carbon composites from both commercial origin and from spent Li-ion batteries and mill scale for the removal of ibuprofen in water.

Zero valent iron/carbon composites were successfully synthesized from commercial iron oxide and graphite (ZVI/C) and also by using graphite obtained from spent Li-ion batteries and iron oxide from mill scale (ZVI/C-X) as a new approach for the valorization of these waste. The composites were synthesized through carbothermic reactions and tested as catalysts for the degradation of ibuprofen from water by Fenton reaction. The optimal conditions for synthesizing ZVI/C composites were a temperature of 1000 °C maintained for 2 h. The structural, and textural features of ZVI/C with different ZVI mass ratios were characterized by different techniques. ZVI/C composites with higher ZVI mass ratios showed higher degradation rates for the removal of ibuprofen both in presence and absence of H2O2. Moreover, ZVI/C-X composite, obtained from industrial waste, showed activity even after four consecutive cycles of use with very low concentration of iron ions in solution after reaction (4.8 mg L-1 after 4 h), which supports the high stability and low Fe-lixiviation of ZVI/C-X composite. The results of this study prove the possibility of synthesizing composites using graphite from spent Li-ion batteries and iron oxide from mill scale, and their potential for the degradation of ibuprofen in water, with comparable activities to those obtained from commercial feedstocks.

Removal of phenol and phosphate from aqueous solutions using activated carbons prepared from oily sludge through physical and chemical activation.

Preparation and characterization of activated carbons (ACs) from oily sludge by physical and chemical activation using steam, ZnCl2 and FeCl3 were investigated. The characteristics of produced adsorbents were determined by iodine number, Brunauer-Emmett-Teller (BET) equation, Fourier transform infrared spectrometry and scanning electron microscopy analyses. Batch adsorption experiments for phenol and phosphate were performed to evaluate the efficiency of adsorbents. The optimum porous structure of adsorbents with a BET surface area of 1,259 m2 g-1, total pore volume of 1.22 cm3 g-1 and iodine number of 994 mg g-1 was achieved by ZnCl2 activation at 500 °C and impregnation ratio of 1:1. The adsorption data were well fitted to the pseudo-second-order kinetic model (R2>0.99) and Freundlich isotherm (R2>0.99). The maximum adsorption capacity of phenol (238 mg g-1) and phosphate (102 mg g-1) based on the Langmuir model was achieved at pH of 6.0 and adsorbent dose of 1 g L-1. Thermodynamic parameters were negative and showed that adsorption of phenol and phosphate onto the AC was feasible, spontaneous and exothermic. The results suggested that prepared AC was an effective adsorbent for removal of phenol and phosphate ions from the polluted water.

Methanol-Promoted Oxidation of Nitrogen Oxide (NOx) by Encapsulated Ionic Liquids.

The removal of nitrogen oxides (NOx) has been extensively studied due to their harmful effects to health and environment. In this work, encapsulated ionic liquids (ENILs) are used as catalysts for the NO oxidation at humid conditions and low temperatures. Hollow carbon capsules (CCap) were first synthesized to contain different amounts of 1-butyl-3-methylimidazolium nitrate IL ([bmim][NO3]), responsible for the catalytic oxidation. Then, the materials were characterized using different techniques, by analyzing microstructure, porosity, elemental composition, and thermal stability. The catalytic performance of ENIL materials was tested for NO conversion at different conditions. Thus, NO concentration was fixed at 2000 ppm at dry and humid conditions. Then, the methanol promotion of the reaction was demonstrated, increasing the NO conversion values in all cases, and the alcohol/water ratio was optimized. The temperature effect was studied as well, using the optimal conditions based on the previous measurements. The results reflect that humid conditions do not have a negative effect in terms of NO conversion when using ENILs, opposite behavior as observed for CCap and traditional catalysts studied before. The low amount of IL inside the material (40% in mass) was found to be the optimum for the task, reaching conversions of almost 45% in near industrial conditions of temperature and O2 and H2O concentrations in the flue gas with a GHSV of 10,000 h-1.

Effect of Activating Agent on the Properties of TiO2/Activated Carbon Heterostructures for Solar Photocatalytic Degradation of Acetaminophen.

Several activated carbons (ACs) were prepared by chemical activation of lignin with different activating agents (FeCl3, ZnCl2, H3PO4 and KOH) and used for synthesizing TiO2/activated carbon heterostructures. These heterostructures were obtained by the combination of the activated carbons with a titania precursor using a solvothermal treatment. The synthesized materials were fully characterized (Wavelength-dispersive X-ray fluorescence (WDXRF), X-ray diffraction (XRD), Scanning electron microscopy (SEM), N2 adsorption-desorption, Fourier transform infrared (FTIR) and UV-visible diffuse reflectance spectra (UV-Vis DRS) and further used in the photodegradation of a target pharmaceutical compound (acetaminophen). All heterostructures were composed of anatase phase regardless of the activated carbon used, while the porous texture and surface chemistry depended on the chemical compound used to activate the lignin. Among all heterostructures studied, that obtained by FeCl3-activation yielded complete conversion of acetaminophen after 6 h of reaction under solar-simulated irradiation, also showing high conversion after successive cycles. Although the reaction rate was lower than the observed with bare TiO2, the heterostructure showed higher settling velocity, thus being considerably easier to recover from the reaction medium.

Photostability and photocatalytic degradation of ionic liquids in water under solar light.

The aim of this work is to study, (i) the photostability of different imidazolium and pyridinium ionic liquids (ILs) in water under solar light; and (ii) the photocatalytic degradation of those ILs in water with TiO2 under solar light. The effects of the type of cation and anion as well as the length of the cationic chain of the imidazolium ILs have been analyzed. These imidazolium-based ILs show high solar stability, slightly decreasing as the length of the cationic chain increases. The anion plays a main role in the stability of ILs under solar light, decreasing in the case of hydrophobic anions. The kind of head group (pyridinium or imidazolium) or the presence of functional groups (allyl, OH) also influence the solar light stability. DFT calculations on the fundamental and excited electronic states of the ILs were carried out to obtain a deeper insight on their photostability. In the case of the photocatalytic degradation of the ILs, complete conversion was achieved for all the ILS tested but mineralization reached 80% at the most. The rate of degradation increased with the length of the alkyl chain while the anion showed little effect. The pyridinium-based IL tested was the easiest to breakdown.

Effects of pH value and calcium hardness on the removal of 1,1,1-trichloroethane by immobilized nanoscale zero-valent iron on silica based supports.

Immobilizing nanoscale zero-valent iron (NZVI) particles on silica-based supports is an effective way to overcome the NZVI aggregation. The pH value and calcium hardness can change the aggregation kinetics and alter the stability of the suspensions of NZVI-silica based materials, thus change the reactivity of these NZVI-silica based materials to remove chlorinated aliphatic hydrocarbons (CAHs). The removal of CAHs by these NZVI-silica based materials includes adsorption by silica based supports and degradation by NZVI particles. Using 1,1,1-TCA and mesoporous hydrated silica (mHS) as model chlorinated aliphatic hydrocarbon (CAH) and silica based support, the effects of pH value and Ca2+ concentration on both the adsorption and adsorption-degradation processes of CAHs by NZVI-silica based materials were studied. The structural and textural features, suspension stability, particle size distribution, and Zeta potential of the materials under various conditions were characterized by different techniques. Both decreasing initial pH value and increasing Ca2+ concentration can reduce the Zeta potential of mHS and lead to the aggregation of mHS particles, thus inhibiting the removal of 1,1,1-TCA via adsorption by mHS through decreasing the number of sites for adsorption. Low initial pH value can accelerate the corrosion of NZVI core and remove the passivation layer, thus promoting the removal of 1,1,1-TCA via adsorption-degradation by NZVI@mHS. Ca2+ can decrease the sites for adsorption and form precipitates which can block mesoporous channels, thus hinder the 1,1,1-TCA removal via adsorption-degradation by NZVI@mHS.

Ag-Coated Heterostructures of ZnO-TiO2/Delaminated Montmorillonite as Solar Photocatalysts.

Heterostructures based on ZnO-TiO2/delaminated montmorillonite coated with Ag have been prepared by sol-gel and photoreduction procedures, varying the Ag and ZnO contents. They have been thoroughly characterized by XRD, WDXRF, UV-Vis, and XPS spectroscopies, and N2 adsorption, SEM, and TEM. In all cases, the montmorillonite was effectively delaminated with the formation of TiO2 anatase particles anchored on the clay layer's surface, yielding porous materials with high surface areas. The structural and textural properties of the heterostructures synthesized were unaffected by the ZnO incorporated. The photoreduction led to solids with Ag nanoparticles decorating the surface. These materials were tested as photocatalysts for the degradation of several emerging contaminants with different nitrogen-bearing chemical structures under solar light. The catalysts yielded high rates of disappearance of the starting pollutants and showed quite stable performance upon successive applications.

Anion effects on kinetics and thermodynamics of CO2 absorption in ionic liquids.

A thermogravimetric technique based on a magnetic suspension balance operating in dynamic mode was used to study the thermodynamics (in terms of solubility and Henry's law constants) and kinetics (i.e., diffusion coefficients) of CO2 in the ionic liquids [bmim][PF6], [bmim][NTf2], and [bmim][FAP] at temperatures of 298.15, 308.15, and 323.15 K and pressures up to 20 bar. The experimental technique employed was shown to be a fast, accurate, and low-solvent-consuming method to evaluate the suitability of the ionic liquids (ILs) to be used as CO2 absorbents. Thermodynamic results confirmed that the solubility of CO2 in the ILs followed the order [bmim][FAP] > [bmim][NTf2] > [bmim][PF6], increasing with decreasing temperatures and increasing pressures. Kinetic data showed that the diffusion coefficients of CO2 in the ILs followed a different order, [bmim][NTf2] > [bmim][FAP] > [bmim][PF6], increasing with increasing temperatures and pressures. These results evidenced the different influence of the IL structure and operating conditions on the solubility and absorption rate of CO2, illustrating the importance of considering both thermodynamic and kinetic aspects to select adequate ILs for CO2 absorption. On the other hand, the empirical Wilke-Chang correlation was successfully applied to estimate the diffusion coefficients of the systems, with results indicating the suitability of this approach to foresee the kinetic performance of ILs to absorb CO2. The research methodology proposed herein might be helpful in the selection of efficient absorption solvents based on ILs for postcombustion CO2 capture.

Encapsulated ionic liquids (ENILs): from continuous to discrete liquid phase.

Encapsulated ionic liquid (ENIL) material was developed, consisting of ionic liquid (IL) introduced into carbon submicrocapsules. ENILs contain >85% w/w of IL but discretized in submicroscopic encapsulated drops, drastically increasing the surface contact area with respect to the neat fluid. ENIL materials were here tested for gas separation processes, obtaining a drastic increase in mass transfer rate.