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• Ni-HAB MOF sensor array provides exceptionally low drift in electrochemical sensors. • MOF-modified solid-contact sensors improve hydroponic nutrient monitoring. • K+, pH, and NO 3 - monitoring in a portable system enables long-term agricultural use. In agricultural contexts, the demand for continuous and precise measurement of multiple ions is crucial. While arrays of solid-contact ion-selective electrodes (SCEs) have been developed previously, there has been limited emphasis on their continuous and long-term monitoring of ions. Addressing this gap, our work introduces an innovative sensor array utilizing Ni-HAB MOF as an ion-to-electron transducer, enabling real-time detection of nitrate, potassium, and pH levels. The sensors exhibit exceptional stability, eliminating the need for frequent recalibration. For instance, the K+-selective sensor displays an unprecedentedly low potential drift of 0.05 µV/h, surpassing existing solid-contact sensors by two orders of magnitude. Similarly, the pH sensor demonstrates a drift of 0.3 µV/h, outperforming competitors by a factor of 100. The NO 3 --selective sensor shows minimal drift at 0.5 µV/h, surpassing comparable sensors by a factor of ten. Additionally, the K+-selective sensor features a sensitivity of 57.8 mV/dec and a LOD of 1.9 µM, while the NO 3 --selective sensor offers a sensitivity of 56.8 mV/dec and a LOD of 6.23 µM. Integrated into a portable array with wireless data transmission, this system enables real-time water quality monitoring in remote areas. Rigorous testing of the developed sensor array in a tailored complex agricultural solution confirms its selective response to target ions even in the presence of interfering ions. Importantly, pH fluctuations do not compromise the precision of the K+ and NO 3 -- selective sensors, highlighting the system's robustness in real-world agricultural settings. [ABSTRACT FROM AUTHOR]

Summary: The impact of ship emissions on the environment cannot be ignored and should be controlled. The possibility of applying seawater electrolysis technology and a novel amide absorbent (BAD, C12H25NO) to the simultaneous desulfurization and denitrification of ship exhaust gas is entirely confirmed by using various seawater resources. Concentrated seawater (CSW) with high salinity can effectively reduce the heat generated during electrolysis and the escape of chlorine. The initial pH of the absorbent can greatly affect the NO removal capacity of the system, and the BAD could keep the pH range suitable for NO oxidation in the system for a long time. The use of fresh seawater (FSW) to dilute the electrolysis of concentrated seawater (ECSW) to make an aqueous oxidant is a more reasonable scheme; the average removal efficiencies of SO2, NO, and NOx were 97.10%, 75.41%, and 74.28%, respectively. The synergistic effect of HCO3−/CO32− and BAD was shown to further restrict NO2 escape.

This case studied the treatment of cheese whey wastewater (CWW) from the Kalleh® dairy industry using a membrane bioreactor (MBR). The coagulation process and activated sludge sections eliminated 26% and 75% of organic matter from CWW with chemical oxygen demand (COD) of 10,000 mg/l, respectively. In the MBR, metal-organic framework (MOF)-modified PSf membranes enhanced the whole system's performance. The flux of water and CWW increased from 157 and 28 (L/m2.h) to 350 and 60 (L/m2.h), respectively, by only 2 wt% MOF concentration. The reduction of COD in the overall system was around 98.8%.

Summary: Biophotoelectrochemistry (BPEC) is an interdisciplinary research field and combines bioelectrochemistry and photoelectrochemistry through the utilization of the catalytic abilities of biomachineries and light harvesters to accomplish the production of energy or chemicals driven by solar energy. The BPEC process may act as a new approach for sustainable green chemistry and waste minimization. This review provides the state-of-the-art introduction of BPEC basics and systems, with a focus on light harvesters and biocatalysts, configurations, photoelectron transfer mechanisms, and the potential applications in energy and environment. Several examples of BPEC applications are discussed including H2 production, CO2 reduction, chemical synthesis, pollution control, and biogeochemical cycle of elements. The challenges about BPEC systems are identified and potential solutions are proposed. The review aims to encourage further research of BPEC toward development of practical BPEC systems for energy and environmental applications.

Summary: There is no efficient wastewater treatment solution for removing organic micropollutants (OMPs), which, therefore, are continuously introduced to the Earth's surface waters. This creates a severe risk to aquatic ecosystems and human health. In emerging water treatment processes based on ion-exchange membranes (IEM), transport of OMPs through membranes remains unknown. We performed a comprehensive investigation of the OMP transport through a single IEM under non-steady-state conditions. For the first time, positron annihilation lifetime spectroscopy was used to study differences in the free volume element radius between anion- and cation-exchange membranes, and between their thicknesses. The dynamic diffusion-adsorption model was used to calculate the adsorption and diffusion coefficients of OMPs. Remarkably, diffusion coefficients increased with the membrane thickness, where its surface resistance was more evident in thinner membranes. Presented results will contribute to the improved design of next-generation IEMs with higher selectivity toward multiple types of organic compounds.

Summary: Oxidative water purification of micropollutants (MPs) can proceed via toxic intermediates calling for procedures for connecting degrading chemical mixtures to evolving toxicity. Herein, we introduce a method for projecting evolving toxicity onto composite changing pollutant and intermediate concentrations illustrated through the TAML/H2O2 mineralization of the common drug and MP, propranolol. The approach consists of identifying the key intermediates along the decomposition pathway (UPLC/GCMS/NMR/UV-Vis), determining for each by simulation and experiment the rate constants for both catalytic and noncatalytic oxidations and converting the resulting predicted concentration versus time profiles to evolving composite toxicity exemplified using zebrafish lethality data. For propranolol, toxicity grows substantially from the outset, even after propranolol is undetectable, echoing that intermediate chemical and toxicity behaviors are key elements of the environmental safety of MP degradation processes. As TAML/H2O2 mimics mechanistically the main steps of peroxidase catalytic cycles, the findings may be relevant to propranolol degradation in environmental waters.

Modified polyvinyl alcohol (PVA) beads serve as effective anaerobic microbe immobilization carriers. PVA beads were mixed with different conductive materials, activated carbon, magnetite, and green tuff stone powder. In this study, modified PVA beads were used to investigate the effect of using, promote methane production, and enhance direct interspecies electron transfer (DIET) on the anaerobic syntrophic degradation of propionate, which is an essential intermediate process for generating methane in anaerobic digesters. The batch experiment showed that PVA mixed with activated carbon had the highest methane conversion rate of 72%, whereas the rates for control (sludge) was 61%. Moreover, the lag time during the second and third feedings was shorter by 5-fold than for the first feeding when modified PVA beads were added. The syntrophic propionate degrading microorganisms in the modified PVA beads was Syntrophobacter and Methanobacterium, either Methanoculleus or Methanosaeta. The modified PVA beads hold at least 10 times larger syntrophs than normal PVA. Therefore, composite PVA with conductive materials can promote methane production, accelerate propionate consumption, and enhance electron transfer in related microbial species.

The reaction kinetic rate and mass transport play an important role in the sizing and scale-up of reactors. The Damköhler's dimensionless number (Da) is the quotient of these effects. A new interpretation of Da as a local property is introduced Da(x,y,z,t). A new graphical methodology is proposed for the sizing and scale-up of unidirectional flow reactors and CSTRs. The partial differential equation (PDE) and algebraic that describe the continuity within these reactors transform into dimensionless variables, and the conversion at the output is expressed as a function of the conditions at the input Da0. The operating conditions as volumetric flow, residence time; design variables as reactor volume; and intrinsic reaction rate are involved in Da0. The equations are solved numerically to develop the design charts Da0 vs X.The design volume is linear with Da0, and the conversion is obtained from the charts (Da0 vs X) or vice versa. Using these charts avoids the analytical or numerical solution of the PDE that governs the unidirectional flow reactors becoming an easy tool for scale-up. The article portrays how to use these diagrams. Reactors with Da0< 0.1 have a low conversion per pass, the charts also allow estimating the number of recirculations required as a function of the overall conversion. Reactors with the same conversion have the same Da0, both laboratory and industrial scale. Then, the Danumber is presented as a fundamental parameter for design and scaling-up these reactors.

Lead is a heavy metal that is bio accumulative and non-biodegradable that poses a threat to our health when it exists in excess in our bloodstream. It has found its way into wastewater from mostly chemical industrial processes. In this article, we investigated the adsorption and hence removal of lead (II) ions from wastewater in order to purify it for re-use in industrial processes or for plant and animal use. We synthesized nano silica hollow spheres (NSHS) and used them as adsorbents to remove lead ions from wastewater. When we characterized the NSHS using X-Ray diffraction, the amorphous nature of silica was evident with average crystal size of 39.5 nm. Scanning electron microscopy was used to determine the morphology of the adsorbent and the particles were found to be spherical in shape within a size range of 100–200 nm. Thermogravimetric analysis was used to determine the mass loss of NSHS which was ~2% at 800 °C. Our experimental results from adsorption studies showed that there was a linear relationship between temperature (27–60 °C) and adsorption efficiency and an inverse relationship between initial metal concentration (50–300 mg/L) and adsorption efficiency. At a maximum temperature of 60 °C and maximum initial metal concentration of 300 mg/L, the adsorption capacity was 200 mg/g and 262 mg/g, respectively while the adsorption efficiency was 99.6% and 87.4%, respectively. Our equilibrium and thermodynamic results revealed that the process was better modelled by the Langmuir adsorption isotherm (qmax = 266.89 mg/g and b = 0.89 L/mg). The adsorption process was both endothermic (ΔH = 97 kJ/mol) and spontaneous (ΔG = -22 kJ/mol). We can conclude that we were able to successfully synthesize NSHS, use them to remove lead (II) ions and the produced NSHS have a capacity that is higher than most other adsorbents investigated by other researchers.

Solidifiers are dry, granular hydrophobic polymers that form physical bonds with hydrocarbons by molecular interactions (hydrogen bonding, London forces), and are used to immobilize hydrocarbon spill propagation and dispersion. CIAgent© is a non-toxic, proprietary polymer blend listed as an “Oil Solidifier” on the EPA's National Contingency Plan Product Schedule for use on hydrocarbon spills in the navigable waterways of United States. CIAgent solidifies the liquid hydrocarbons through a rapid transformation into a cohesive rubber-like inert mass upon contact and retains the liquid for easier removal and disposal. The objective of this paper is to determine the effectiveness of the solidifier with a variety of hydrocarbon liquids that could be encountered in an oil spill scenario. The effectiveness of the solidifier was characterized in terms of the application rate, temperature change, solubility parameters and solidification time for a variety of hydrocarbon liquids (e. g., gasoline, diesel fuel, crude oil) that could be encountered by measuring the heat of solidification using a solution calorimeter. A thermogram was obtained and the heat of solidification was calculated using the temperature difference upon solidification. The temperature change and the degree of swelling in the solidifier were used to determine the solubility parameter of the solidifier (6.77 Hildebrands). The heat of solidification value was used to determine the ease and speed of the solidification of the hydrocarbon liquids. Solidification times ranged from 40 to 120 s for the liquids tested. The average application ratio in weight of solidifier to weight of hydrocarbon ranged was 3.35.

The increase in price of the available refined petroleum products for local consumption in Nigeria had led to the emergence of indigenous technology for petroleum refining in some parts of the Niger Delta region. This study, therefore characterized and quantified artisanal refineries’ gaseous emissions for possible air pollutants based on various unit operations involved and evaluated their impacts. It measured the emissions directly from source using E8500 Portable Combustion Analyzer. It also categorized oven sizes/processing capacity of the refineries into various ranges in order to estimate emissions according to processing capacity. The result revealed that; pollutants emission varied significantly between the unit operations and increased with increase in processing capacity. When the emissions were compared with daily limits set by the Environmental Guidelines and Standard for Petroleum Industry in Nigeria (EGASPIN) 2002, the emissions (CO, NOx, and SO2) breached the available set limits. While with the Federal Environmental Protection Agency (FEPA), 1991 set limits for emissions from stationary source; HC and CO breached their limits. SO2 and H2S breached their lower limits but were below the upper limit, while NOx emissions were found within its set limit. The study concluded that, Nigeria Artisanal Petroleum Refineries are sources of air pollution, as they impact the host environment.

Abattoir wastewater generated from various meat processing operations in several developing countries pose a serious threat to the environment. Consequently, there is urgent need to reduce the impact of environmental pollution from it. Coagulation techniques have been recommended and used by many researchers successfully in treating wastewater, therefore an investigation of possible use of chito-protein extracted from crab shell (locally sourced) was used as a coagulant for treating abattoir wastewater. Coagulation experiments were carried out using jar-test procedure to investigate the influence of pH, time of settling, temperature and adsorbent dosage for coagulation of BOD, COD, Turbidity and Colour from the wastewater sample. To determine the interaction effect of the various process variables, Response Surface Method (RSM) was used in the optimization of the process variables. To determine the effectiveness of the coagulant, pre and post characterization of the wastewater samples were undertaken, the result of the post characterization of the wastewater sample indicated that most of the water quality parameters except Iron were within WHO standard. The Total Suspended Solid (TSS), for instance stood at 564.6 mg/L and 29 mg/L respectively for pre and post characterisation, the value of 29 mg/L of the post characterization was below the WHO recommended value of 30 mg/L. The predicted responses and the experimental values correlated significantly, an indicator that RSM optimization method used in this study is suitable in modelling the process variables. The result of the study further shows that optimum process variable is dependent on the solution pH (acidic), coagulant dosage of 2–3g, settling time of 25–30 min and operating temperature from 323K to 333K. The coagulant used in this study, when compared with previous studies have shown to have strong potential for use as a coagulant and as an alternative to chemical coagulants in the treatment of abattoir wastewater.

Summary: It is still challenging to develop strongly alkali-resistant catalysts for selective catalytic reduction of NOx with NH3. It is generally believed that the maintenance of acidity is the most important factor because of neutral effects of alkali. This work discovers that the redox properties rather than acidity play decisive roles in improving alkali resistance of some specific catalyst systems. K-poisoned Fe-decorated SO42−-modified CeZr oxide (Fe/SO42−/CeZr) catalysts show decreased acidity but reserve the high redox properties. The higher reactivity of NHx species induced by K poisoning compensates for the decreased amount of adsorbed NHx, leading to a desired reaction efficiency between adsorbed NHx and nitrate species. This study provides a unique perspective in designing an alkali-resistant deNOx catalyst via improving redox properties and activating the reactivities of NHx species rather than routinely increasing acidic sites for NHx adsorption, which is of significance for academic interests and practical applications.

The present work provides to treat real oily saline wastewater released from drilling oil sites by the use of electrocoagulation technique. Aluminum tubes were utilized as electrodes in a concentric manner to minimize the concentrations of 113400 mg TDS/L, 65623 mg TSS/L, and the ions of 477 mg HCO3/L, 102000 mg Cl/L and 5600 mg Ca/L presented in real oily wastewater under the effect of the operational parameters (the applied current and reaction time) by making use of the central composite rotatable design. The final concentrations of TDS, TSS, HCO3, Cl, and Ca that obtained were 93555 ppm (17.50%), 11011 ppm (83.22%), 189ppm (60.38%), 80000ppm (22%), and 4200 ppm (25%), respectively, under the optimum values of the operational parameters (1.625 Amps and 40 min). In spite of the low removal percentages of some pollutants, the present study proved the ability of this novel designed reactor for treating high saline real oily wastewater in accordance with the operational parameters. This prove the capability of the use of it as a pre-treatment of other conventional methods.

The amount of palm oil mill residues increases rapidly and will become a severe problem in the future. One potential technique for alleviating this concerning environmental problem is to convert these residues into biochar by the pyrolysis process. Pyrolysis of three types of palm oil mill residues (namely, palm kernel shells, empty palm fruit bunches, and oil palm fibers) was conducted in a fixed bed reactor at 500 °C and 2 L/min of nitrogen flow rate for 60 min. The optimization of biochar production was performed using the Box-Behnken design and analyzed using response surface methodology. The effects of three potential factors, including pyrolysis temperatures, nitrogen flow rates, and biomass particle sizes, were studied. The results showed that the highest biochar yield (44.91 wt%) was obtained from pyrolysis of palm kernel shells at 525 °C with a nitrogen flow rate of 2 L/min and a particle size of 750 μm. Application of biochar produced from palm kernel shells for carbon dioxide capture was tested in a packed bed adsorber of 3.0 g of biochar sample by flowing 1,400 ppm of carbon dioxide in the gas feed mixture at 2.5 L/min. The capacity of the biochar sample for CO2 adsorption was 0.46 mmol/g.

Microbubble technology dramatically raises the efficiency of the flotation and aeration processes of water treatment plants (WTPs), which see extensive use in developed countries. A local institution, Indonesia Water Institute, has tried to investigate microbubble technology intended for lab-scale WTP. However, the current reactor system does not yet meet the microbubble criteria, especially as it has had few investigations of its abilities in flotation and aeration. This study aims to analyze the effect of size variations that affect the rising velocity and mass transfer coefficient (kLa) of aeration contact time. Three local spargers were used to produce microbubbles. Bubble diameters were measured optically and analyzed using ImageJ software. The dissolved oxygen (DO) concentration was measured every minute using an automated sensor so that the kLa could be determined. Of the three spargers, the smallest bubble size was produced by the vortex type with an average bubble diameter of 89 μm and the slowest rising velocity of 17.67 m/h. It also yielded the highest kLa of 0.297/min, which gave an aeration contact time of 3.64 minutes. The experimental uses of three local spargers revealed that the smaller the microbubble diameter, the higher the mass transfer coefficient in flotation and aeration processes. This research can be the basis for developing microbubble technology for WTP in Indonesia.

A bench-scale model of a partially packed upflow anaerobic fixed film (UAF) reactor was set up and operated at five different hydraulic retention times (HRTs) of (17, 14, 10, 8, and 5) days. The reactor was fed with synthetic rubber wastewater consisting of a chemical oxygen demand (COD) concentration of 6355–6735 mg/L. The results were analyzed using the Monod model, the Modified Stover-Kincannon models, and the Grau Second-Order Model. The Grau Second-Order model was found to best fit the experimental data. The biokinetic constant values, namely the growth yield coefficient (Y) and the endogenous coefficient (Kd) were 0.027 g VSS/g COD and 0.1705 d−1, respectively. The half-saturation constant (Ks) and maximum substrate utilization rate (K) returned values of 84.1 mg/L and 0.371 d−1, respectively, whereas the maximum specific growth rate of the microorganism (μmax) was 0.011 d−1. The constants, Umax and KB, of the Stover-Kincannon model produced values of 6.57 g/L/d and 6.31 g/L/d, respectively. Meanwhile, the average second-order substrate removal rate, ks(2), was 105 d−1. These models gave high correlation coefficients with the value of R2 = 80–99% and these indicated that these models can be used in designing UAF reactor consequently predicting the behaviour of the reactor.

Iron chelate liquid redox sulfur recovery (LRSR) has been one of the most frequently recommended technologies for the oxidation of H2S in natural gas into elemental sulfur, particularly when the acid gas has a high CO2/H2S molar ratio. The process is however known to suffer from extensive oxidative ligand degradation that results in high operational costs. Moreover, poor biodegradability or toxicity of the existing ligand has become a concern. In this research, we demonstrated that gluconate, a naturally greener ligand, when coupled with manganese as the metal, has considerable potential to be a better redox agent. Manganese gluconate solution was more resistant against ligand degradation compared with iron NTA. As required, aerated solution was capable of converting dissolved NaHS into elemental sulfur. At sufficiently high pH, manganese gluconate solutions were stable enough from precipitation of manganese hydroxide, carbonate, or sulfides. An equilibrium calculation has been developed to understand the precipitation behavior.

Emissions of nitrogen oxides such as NO and NO2, which are commonly known as NOx, are threats to human existence and cause environmental problems. Mainly, two techniques have been developed to drastically reduce these emissions, which are dry and wet processes. The wet process has several advantages, major identifiable advantages are the adaptability to the flue gas, low operating temperatures and no poisoning and inactivation catalyst. Also, a mixture of hydrogen peroxide and nitric acid are used as absorbents solution for NOx reduction in the wet process. The advantages of using this mixture include the ability to reduce the negative effect of NOx and does not contaminate the scrubbing solution. In addition, nitric acid has an economical advantage in the process considering the fact that it is produced in the process. Finally, it can be conducted at ambient temperature. This study furthermore used a mixture of hydrogen peroxide and nitric acid solutions as an absorbent to reduce NOx in hollow fiber membrane modules. The hydrogen peroxide oxidized HNO2 to nitric acid, while enhances the oxidation through an autocatalytic reaction. The effects of the feed gas flow rate, hydrogen peroxide concentrations and number of fibers on the NOx reduction, absorbed NOx and flux were varied to study. The experimental results showed that the increase in the feed gas flow rate from 100 to 200 mL/min decreased NOx reduction from about 98 to 94% but increased the absorbed NOx and flux from about 0.13 to 0.255 mmol/h and 0.85–1.63 mmol/m2.h, respectively The increase in proportion of NOx in the feed gas effect was dominant than the increase in absorbed NOx. An increase in hydrogen peroxide concentration from 0.5 to 10 wt.% in the absorbent solutions increased NOx reduction, absorbed NOx and flux from about 94 to 98%, 0.257–0.267 mmol/h and 1.09–1.13 mmol/m2.h, respectively. Additionally, the H2O2 plays an important role in enhancing HNO2 oxidation to HNO3. Furthermore, an increase in the number of fibers from 50 to 150 in the membrane module increased NOx reduction and absorbed NOx from 86 to 97% and 0.23–0.27 mmol/h. Flux decreased from 2.98 to 1.13 mmol/m2.h due to increment in the gas-liquid contact surface area.

Abstract: The aim of this work consists in a feasibility study to understand how arsenate ions could be removed from contaminated water by sorption onto chitosan, a biopolymer extracted from the wastes of the seafood industries. Firstly, a batch adsorption study investigates different models, namely Langmuir, Freundlich, Tempkin, and Redlich–Peterson. The sorption mechanism is shown to be sorption by an electrostatic attraction, with thermodynamic parameters indicating an exothermic and spontaneous reaction. The main influencing parameters are the temperature, the pH and the presence of other ions. Secondly, a semi-dynamic membrane process is proposed: a stirred batch reactor is coupled with a microfiltration immersed-membrane. A mass balance model is used to describe the adsorption process and the breakthrough curves are well simulated. [Copyright &y& Elsevier]