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• A microwave-assisted protocol towards biofuel precursor furfural (FF) was implemented. • Namely almond hull (AH), olive stone (OS), and wine-derived by-products were evaluated. • Mild conditions (150 °C, 10–20 min) and green strategies (AlCl 3 ·6H 2 O) were applied. • Noted molar yield (38–42 %) and selectivity (50–60 %) were achieved from AH and OS. • Sustainable waste management and biorefinery approaches were assessed. This work outlines the first microwave (MW)-assisted protocol for the production of biofuel precursor furfural (FF) from the raw agricultural waste almond hull (AH), olive stone (OS), and the winemaking-derived grape stalk (GS), grape marc (GM) and exhausted grape marc (EGM) through a one-pot synthesis process. To enhance the overall yield, a catalytic process was firstly developed from xylose, major constituent of hemicellulose present in lignocellulosic biomass. This method afforded FF with 100 % selectivity, yielding over 85 % in isolated product when using H 2 SO 4 , as opposed to a 37 % yield with AlCl 3 ·6H 2 O, at 150 °C in only 10 min. For both catalysts, the developed methodology was further validated, proving adaptable and efficient in producing the targeted FF from the aforementioned lignocellulosic raw materials. More specifically, the employment of AlCl 3 ·6H 2 O resulted in the highest selectivity (up to 89 % from GM) and FF yield (42 % and 39 % molar from OS and AH, respectively), maintaining notable selectivity for the latter (61 and 48 % from AH and OS). At this regard, and considering the environmental factor of sustainability, it is important to point out the role of AlCl 3 ·6H 2 O in contrast to H 2 SO 4 , thus mitigating detrimental substances. This study provides an important management of agricultural waste through sustainable practises for the development of potential bio-based chemicals, aligning with Green Chemistry and process intensification principles. [ABSTRACT FROM AUTHOR]

• 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.

Summary: The light-harvesting complex II of Bryopsis corticulans (B-LHCII), a green alga, differs from that of spinach (S-LHCII) in chlorophyll (Chl) and carotenoid (Car) compositions. We investigated ultrafast excitation dynamics of B-LHCII with visible-to-near infrared time-resolved absorption spectroscopy. Absolute fluorescence quantum yield (ΦFL) of LHCII and spectroelectrochemical (SEC) spectra of Chl a and b were measured to assist the spectral analysis. Red-light excitation at Chl Qy-band, but not Car-band, induced transient features resembling the characteristic SEC spectra of Chl a⋅+ and Chl b⋅−, indicating ultrafast photogeneration of Chl-Chl charge transfer (CT) species; ΦFL and 3Car∗ declined whereas CT species increased upon prolonging excitation wavelength, showing positive correlation of 1Chl∗ deactivation with Chl-Chl CT formation. Moreover, ultrafast Chl b-to-Chl a and Car-to-Chl singlet excitation transfer were illustrated. The red-light induction of Chl-Chl CT species, as also observed for S-LHCII, is considered a general occurrence for LHCIIs in light-harvesting form.

Summary: Persulfate-based nonradical oxidation processes are appealing in water treatment for the efficient and selective degradation of trace contaminants in complex water matrices. However, there is still lacking of systematic understanding of the relationship between multiple nonradical pathways and the active sites of catalyst. Herein, a single-atom Cu catalyst with saturated Cu-N4 sites on a carbon substrate (SA-Cu-NC) was constructed to activate peroxymonosulfate (PMS), which exhibited high catalytic performance and selectivity for pollutant degradation in different water conditions. Combined with the results of density functional theory (DFT) calculations, the electron-rich area around Cu site and the electron-poor area around C site in the saturated Cu-N4 configuration could efficiently adsorb and activate PMS, which promoted pollutant degradation through the oxidation of singlet oxygen (1O2) and electron transfer process, respectively. This study advances the understanding of the saturated coordination structure of metals and the superiority of multiple nonradical pathways in wastewater treatment.

Summary: Assessment of water and soil quality is critical for the health, economy, and sustainability of any community. The release of a range of life-threatening pollutants from agriculture, industries, and the residential communities themselves into the different water resources and soil requires of analytical methods intended for their detection. Given the challenge that represents coping with the monitoring of such a diverse and large number of compounds (with over 100,000 chemicals registered, yet in continuous increase), holistic solutions such as electronic tongues (ETs) are emerging as a promising tool for a sustainable, simple, and green monitoring of soil and water resources. In this direction, this review aims to present and critically provide an overview of the basic concepts of ETs, followed by some relevant applications recently reported in the literature in environmental analysis, more specifically, the monitoring of water and wastewater, their quality and the detection of water pollutants as well as soil analysis.

Summary: Quantification of odor emissions in wastewater treatment plants (WWTPs) is key to minimize odor impact to surrounding communities. Odor measurements in WWTPs are usually performed via either expensive and discontinuous olfactometry hydrogen sulfide detectors or via fixed electronic noses. We propose a portable lightweight electronic nose specially designed for real-time odor monitoring in WWTPs using small drones. The so-called RHINOS e-nose allows odor measurements with high spatial resolution, and its accuracy is only slightly worse than that of dynamic olfactometry. The device has been calibrated using odor samples collected in a WWTP in Spain over a period of six months and validated in the same WWTP three weeks after calibration. The promising results obtained support the suitability of the proposed instrument to identify the odor sources having the highest emissions, which may give a useful indication to the plant managers as regards odor control and abatement.

Summary: Current photocatalytic uranium (U) extraction methods have intrinsic obstacles, such as the recombination of charge carriers, and the deactivation of catalysts by extracted U. Here we show that, by applying a bias potential on the photocatalyst, the photoelectrochemical (PEC) method can address these limitations. We demonstrate that, owing to efficient spatial charge-carriers separation driven by the applied bias, the PEC method enables efficient and durable U extraction. The effects of multiple operation conditions are investigated. The U extraction proceeds via single-step one-electron reduction, resulting in the formation of pentavalent U, which can facilitate future studies on this often-overlooked U species. In real seepage water the PEC method achieves an extraction capacity of 0.67 gU m−3·h−1 without deactivation for 156 h continuous operation, which is 17 times faster than the photocatalytic method. This work provides an alternative tool for U resource recovery and facilitates future studies on U(V) chemistry.

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: The bio-based lactic acid (LA) and the common metal ion chelating agent iminodiacetic acid (IDA) are used to design and prepare a polymeric sustained-release Pb2+ chelating agent by a brief one-step reaction. After the analysis on theoretical calculation for this reaction, poly(lactic acid-iminodiacetic acid) [P(LA-co-IDA)] with different monomer molar feed ratios is synthesized via direct melt polycondensation. P(LA-co-IDA) mainly has star-shaped structure, and some of them have two-core or three-core structure. Thus, a possible mechanism of the polymerization is proposed. The degradation rate of P(LA-co-IDA)s can reach 70% in 4 weeks. The change of IDA release rate is consistent with the trend of the degradation rate, and the good Pb2+ chelating performance is confirmed. P(LA-co-IDA) is expected to be developed as a lead poisoning treatment drug or Pb2+ adsorbent in the environment with long-lasting effect, and this research provides a new strategy for the development of such drugs.

Summary: Flocculation is a mainstream technology for the provision of safe drinking water but is limited due to the ineffectiveness of conventional flocculants in removing trace low-molecular-weight emerging contaminants. We described a synthesis strategy for the development of high-performance nanoflocculants (hydrophobic-organic-chain-modified metal hydroxides [HOC-M]), imitating surfactant-assembling nano-micelles, by integration of long hydrophobic chains with traditional inorganic metal (Fe/Al/Ti)-based flocculants. The core-shell nanostructure was highly stable in acidic stock solution and transformed to meso-scale coagulation nuclei in real surface water. In both jar and continuous-flow tests, HOC-M was superior over conventional flocculants in removing many contaminants (turbidity, UV254, and DOC: >95%; TP and NO3-N: >90%; trace pharmaceuticals [initial concentration: 100 ng/L]: >80%), producing flocs with better structural and dewatering properties, and lowering the environmental risk of metal leaching. The rationally designed nanoflocculants have large application potential, as a solution to increasing public concern about micro-pollutants and increasing water quality requirements.

Summary: Catechol is speculated to be a potential precursor of environmentally persistent free radicals (EPFRs) in the atmosphere. EPFRs absorbed on PM2.5 have attracted public attention because their toxicity is similar to cigarette smoke. In this study, we found that catechol could produce EPFRs, which were oxygen-centered phenoxy and semiquinone radicals. These free radical species had half-lives of up to 382 days. CaO, CuO, and Fe2O3 markedly promoted EPFR formation from catechol. The valence states of Cu and Fe changed during the photochemical reactions of catechol but no valence state changed for Ca. Alkaline nature of CaO is possibly the key for promoting the free radical formations through acid-base reactions with catechol. In addition to hydroxyl free radicals, hydrogen free radicals and superoxide anions formed from the photochemical reactions of catechol were first discovered. This is of concern because of the adverse effects of these free radicals on human health.

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.

Air pollutant data are compositional in character because they describe quantitatively the parts of a whole (atmospheric composition). However, it is common to use air pollutant concentrations in statistical models without considering this characteristic of the data and, therefore, without control of common statistical problems, such as spurious correlations and subcompositional incoherence. This paper now proposes a daily multivariate spatio-temporal model with a compositional approach. The air pollution spatio-temporal model is based on a dynamic linear modelling framework with Bayesian inference. The novel modelling methodology was applied in an urban area for carbon monoxide (CO, mg·m−3), sulfur dioxide (SO2, μg·m−3), ozone (O3, μg·m−3), nitrogen dioxide (NO2, μg·m−3), and particulate matter less than 2.5 μm in aerodynamic diameter (PM2.5, μg·m−3). The proposal complemented and improved the conventional approach in air pollution modelling. The main improvements come from a fast multivariate data description, high spatial-correlation, and adequate modelling of air pollutants with high variability.

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.