Recent advances in eco-friendly technology for decontamination of pulp and paper mill industrial effluent: a review.

The economic development of a country directly depends upon industries. But this economic development should not be at the cost of our natural environment. A substantial amount of water is spent during paper production, creating water scarcity and generating wastewater. Therefore, the Pollution Control Board classifies this industry into red category. Water is used in different papermaking stages such as debarking, pulping or bleaching, washing, and finishing. The wastewater thus generated contains lignin and xenobiotic compounds such as resin acids, chlorinated lignin, phenols, furans, dioxins, chlorophenols, adsorbable organic halogens (AOX), extractable organic halogens (EOCs), polychlorinated biphenyls, plasticizers, and polychlorinated dibenzodioxins. Nowadays, several microorganisms are used in the detoxification of these hazardous effluents. Researchers have found that microbial degradation is the most promising treatment method to remove high biological oxygen demand (BOD) and chemical oxygen demand (COD) from wastewater. Microorganisms also remove AOX toxicity, chlorinated compounds, suspended solids, color, lignin, derivatives, etc. from the pulp and paper mill effluents. But in the current scenario, mill effluents are known to deteriorate the environment and therefore it is highly desirable to deploy advanced technologies for effluent treatment. This review summarizes the eco-friendly advanced treatment technologies for effluents generated from pulp and paper mills.

Assessment of Halogen Off-Center Point-Charge Models Using Explicit Solvent Simulations.

Compounds containing halogens can form halogen bonds (XBs) with biological targets such as proteins and membranes due to their anisotropic electrostatic potential. To accurately describe this anisotropy, off-center point-charge (EP) models are commonly used in force field methods, allowing the description of XBs at the molecular mechanics and molecular dynamics level. Various EP implementations have been documented in the literature, and despite being efficient in reproducing protein-ligand geometries and sampling of XBs, it is unclear how well these EP models predict experimental properties such as hydration free energies (ΔGhyd), which are often used to validate force field performance. In this work, we report the first assessment of three EP models using alchemical free energy calculations to predict ΔGhyd values. We show that describing the halogen anisotropy using some EP models can lead to a slight improvement in the prediction of the ΔGhyd when compared with the models without EP, especially for the chlorinated compounds; however, this improvement is not related to the establishment of XBs but is most likely due to the improvement of the sampling of hydrogen bonds. We also highlight the importance of the choice of the EP model, especially for the iodinated molecules, since a slight tendency to improve the prediction is observed for compounds with a larger σ-hole but significantly worse results were obtained for compounds that are weaker XB donors.

Realism-based assessment of the efficacy of potassium peroxymonosulphate on Stenotrophomonas maltophilia biofilm control.

The potential of pentapotassium bis(peroxymonosulphate) bis(sulphate) (OXONE) to control biofilms in drinking water distribution systems (DWDS) was evaluated and compared to chlorine disinfection. Mature biofilms of drinking water (DW)-isolated Stenotrophomonas maltophilia were formed using a simulated DWDS with a rotating cylinder reactor (RCR). After 30 min of exposure, OXONE at 10 × minimum bactericidal concentration (MBC) caused a significant 4 log reduction of biofilm culturability in comparison to the unexposed biofilms and a decrease in the number of non-damaged cells below the detection limit (4.8 log cells/cm2). The effects of free chlorine were restricted to approximately 1 log reduction in both biofilm culturability and non-damaged cells. OXONE in synthetic tap water (STW) at 25 ºC was more stable over 40 days than free chlorine in the same conditions. OXONE solution exhibited a disinfectant decrease of about 10% of the initial concentration during the first 9 days, and after this time the values remained stable. Whereas possible reaction of chlorine with inorganic and organic substances in STW contributed to free chlorine depletion of approximately 48% of the initial concentration. Electron paramagnetic resonance (EPR) spectroscopy studies confirmed the presence of singlet oxygen and other free radicals during S. maltophilia disinfection with OXONE. Overall, OXONE constitutes a relevant alternative to conventional DW disinfection for effective biofilm control in DWDS.

Extensive comparison of methods for removal of organic halogen compounds from pharmaceutical process wastewaters with life cycle, PESTLE, and multi-criteria decision analyses.

Recycling and disposing wastewater from the pharmaceutical industry are of utmost importance in mitigating chemical waste generation, where unmanaged hazardous waste fluxes could cause massive environmental damage. Air stripping, steam stripping, distillation, and incineration offer significant emission reduction potentials for pharmaceutical applications; however, selecting specific process units is a complicated task due to the high number of influencing screening criteria. The mentioned chemical processes are modelled with the Aspen Plus program. This study examines the environmental impacts of adsorbable organic halogens (AOX) containing pharmaceutical process wastewater disposal by conducting life cycle impact assessments using the Product Environmental Footprint (PEF), IMPACT World + Endpoint V1.01, and Recipe 2016 Endpoint (H) V1.06 methods. The results show that the distillation-based separation of AOX compounds is characterized by the most favourable climate change impact and outranks the PEF single score of air stripping, steam stripping, and incineration by 6.3%, 29.1%, 52.0%, respectively. The energy-intensive distillation technology is further evaluated by considering a wide selection of energy sources (i.e., fossil fuel, nuclear, solar, wind onshore, and wind offshore) using PESTLE (Political, Economic, Social, Technological, Legal, Environmental) analysis combined with multi-criteria decision support to determine the most beneficial AOX disposal scenario. The best overall AOX regeneration performance and lowest climate change impact (7.25 × 10-3 kg CO2-eq (1 kg purified wastewater)-1) are obtained by supplying variable renewable electricity from onshore wind turbines, reaching 64.87% carbon emission reduction compared to the baseline fossil fuel-based process alternative.

Insights into the impacts of chloride ions on the oxidation of 2,4-dinitrotoluene using ferrous activated persulfate: Removal efficiency, reaction mechanism, transformation pathway, and toxicity assessment.

Persulfate/Fe2+-based advanced oxidation processes are widely used to treat water contaminated with 2,4-dinitrotoluene (DNT). However, the oxidation of DNT by persulfate/Fe2+ in the presence of the chloride ion (Cl⁻) has not been addressed, and the transformation pathways and toxicities of the intermediate products remain unclear. In this study, the effect of different Cl⁻ concentrations on the oxidation of DNT was investigated by persulfate/Fe2+. After the addition of 1.0 mM Cl⁻ and 6 h of oxidation, the removal efficiency of DNT increased by 68.5%. Scavenging experiments and an electron spin resonance analysis suggested that Cl⁻ caused hydroxyl radicals to increase in content in the persulfate/Fe2+ system, thus promoting the removal of DNT. Eight intermediate products of DNT were accurately detected using high-resolution mass spectrometry, and the transformation pathways of DNT were proposed, including hydroxylation/oxidation, elimination of the nitro group, and chlorination process. The acute and chronic toxicities of the intermediate products decreased during the oxidation process, but chlorinated by-products posed a higher toxicological risk. This result is vital for the practical application and environmental safety evaluation of persulfate/Fe2+-based advanced oxidation.

Three for the Price of One: Concomitant I⋯N, I⋯O, and I⋯π Halogen Bonds in the Same Crystal Structure.

The ditopic molecule 3-(1,3,5-trimethyl-1H-4-pyrazolyl)pentane-2,4-dione (HacacMePz) combines two different Lewis basic sites. It forms a crystalline adduct with the popular halogen bond (XB) donor 2,3,5,6-tetrafluoro-1,4-diiodobenzene (TFDIB) with a HacacMePz:TFDIB ratio of 2:3. In a simplified picture, the topology of the adduct corresponds to a hcb net. In addition to the expected acetylacetone keto O and pyrazole N acceptor sites, a third and less common short contact to a TFDIB iodine is observed: The acceptor site is again the most electron-rich site of the pyrazole π-system. This iminic N atom is thus engaged as the acceptor in two orthogonal halogen bonds. Evaluation of the geometric results and of a single-point calculation agree with respect to the strength of the intermolecular contacts: The conventional N⋯I XB is the shortest (2.909(4) Å) and associated with the highest electron density (0.150 eÅ-3) in the bond critical point (BCP), followed by the O⋯I contact (2.929(3) Å, 0.109 eÅ-3), and the π contact (3.2157(3) Å, 0.075 eÅ-3). If one accepts the idea of deducing interaction energies from energy densities at the BCP, the short contacts also follow this sequence. Two more criteria identify the short N⋯I contact as the most relevant: The associated C-I bond is significantly longer than the database average, and it is the only intermolecular interaction with a negative total energy density in the BCP.

Sulfur and chlorine budgets control the ore fertility of arc magmas.

Continental arc magmas supply the ore-forming element budget of most globally important porphyry-type ore deposits. However, the processes enabling certain arc segments to preferentially generate giant porphyry deposits remain highly debated. Here we evaluate the large-scale covariation of key ore-forming constituents in this setting by studying silicate melt inclusions in volcanic rocks from a fertile-to-barren segment of the Andean Southern Volcanic Zone (33-40 °S). We show that the north-to-south, fertile-to-barren gradient is characterized by a northward increase in S and Cl concentrations and a simultaneous decrease in Cu. Consequently, we suggest that the concentration of S and Cl rather than the concentration of ore metals regulates magmatic-hydrothermal ore fertility, and that the loss of volatiles prior to arrival in the upper crust impacts ore-forming potential more than magmatic sulfide saturation-related ore metal scavenging.

Low-Cost Potentiometric Sensor for Chloride Measurement in Continuous Industrial Process Control.

Recently, the new updates in legislation about drinking water control and human health have increased the demand for novel electrochemical low-cost sensors, such as potentiometric ones. Nowadays, the determination of chloride ion in aqueous solutions has attracted great attention in several fields, from industrial processes to drinking water control. Indeed, chloride plays a crucial role in corrosion, also influencing the final taste of beverages, especially coffee. The main goal is to obtain devices suitable for continuous and real-time analysis. For these reasons, we investigated the possibility to develop an easy, low-cost potentiometric chloride sensor, able to perform analysis in aqueous mediums for long immersion time and reducing the need of periodic calibration. We realized a chloride ion selective electrode made of Ag/AgCl sintered pellet and we tested its response in model solutions compatible with drinking water. The sensor was able to produce a stable, reproducible, and accurate quantification of chloride in 900 s, without the need for a preliminary calibration test. This opens the route to potential applications of this sensor in continuous, in situ, and real time measurement of chloride ions in industrial processes, with a reduced need for periodic maintenance.

Halogen content relative to the chemical and biochemical composition of fifteen marine macro and micro algae: nutritional value, energy supply, antioxidant potency, and health risk assessment.

Marine algae have made a strong contribution to global food security in the future. This study is the first report describing the concentration, pathways, and interactions of halogens in 15 species of marine algae collected from the Eastern Harbor in Alexandria, Egypt, relative to 22 key variables. The relationship between halogen content and chemical and biochemical parameters was studied through multivariate analysis. Among all the tested algae, the iodine content was the lowest (2.53-3.00 µg/g). The range of fluoride and chloride in macroalgae (1.12-1.70 and 0.10-0.46 mg/g) was smaller than that of microalgae (0.10-0.46 and 1.48-3.17 mg/g). The bromide content in macroalgae (0.36-5.45 mg/g) was higher than that in microalgae (0.40-0.76 mg/g). The halogen content in macroalgae was arranged in the order of Br > F > Cl > I. In addition, the biochemical parameters such as carbohydrates, proteins, lipids, and certain heavy metals (Fe, Zn, Cu, Mn, Pb, Ni, Co, Cd, and Cr) were determined. Calories, energy, total antioxidant activity (TAC), K/Na, and ion quotient amounts were estimated. The results showed that the green seaweed species had the highest TAC content. In most of the studied algal species, the calculated ion quotient referred to their likelihood of overcoming high blood pressure. The estimated daily intake (EDI) of algae showed no adverse effects on human health. Most of the research variables are below the acceptable WHO/FAO level. Generally, the calorie content of the selected algae is less than 2 kcal, which makes the algae considered an alternative source of healthy food to reduce obesity.Graphical abstract.

In Situ Assessment of Intrinsic Strength of X-I⋯OA-Type Halogen Bonds in Molecular Crystals with Periodic Local Vibrational Mode Theory.

Periodic local vibrational modes were calculated with the rev-vdW-DF2 density functional to quantify the intrinsic strength of the X-I⋯OA-type halogen bonding (X = I or Cl; OA: carbonyl, ether and N-oxide groups) in 32 model systems originating from 20 molecular crystals. We found that the halogen bonding between the donor dihalogen X-I and the wide collection of acceptor molecules OA features considerable variations of the local stretching force constants (0.1-0.8 mdyn/Å) for I⋯O halogen bonds, demonstrating its powerful tunability in bond strength. Strong correlations between bond length and local stretching force constant were observed in crystals for both the donor X-I bonds and I⋯O halogen bonds, extending for the first time the generalized Badger's rule to crystals. It is demonstrated that the halogen atom X controlling the electrostatic attraction between the σ -hole on atom I and the acceptor atom O dominates the intrinsic strength of I⋯O halogen bonds. Different oxygen-containing acceptor molecules OA and even subtle changes induced by substituents can tweak the n → σ ∗ (X-I) charge transfer character, which is the second important factor determining the I⋯O bond strength. In addition, the presence of the second halogen bond with atom X of the donor X-I bond in crystals can substantially weaken the target I⋯O halogen bond. In summary, this study performing the in situ measurement of halogen bonding strength in crystalline structures demonstrates the vast potential of the periodic local vibrational mode theory for characterizing and understanding non-covalent interactions in materials.

The application of new HARD-descriptor available from the CORAL software to building up NOAEL models.

Continuous QSAR models have been developed and validated for the prediction of no-observed-adverse-effect (NOAEL) in rats, using training and test sets from the Fraunhofer RepDose® database and EFSA's Chemical Hazards Database: OpenFoodTox. This paper demonstrates that the HARD index, as an integrated attribute of SMILES, improves the prediction power of NOAEL values using the continuous QSAR models and Monte Carlo simulations. The HARD-index is a line of eleven symbols, which represents the presence, or absence of eight chemical elements (nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine) and different kinds of chemical bonds (double bond, triple bond, and stereo chemical bond). Optimal molecular descriptors calculated with the Monte Carlo technique (maximization of correlation coefficient between the descriptor and endpoint) give satisfactory predictive models for NOAEL. Optimal molecular descriptors calculated in this way with the Monte Carlo technique (maximization of correlation coefficient between the descriptor and endpoint) give amongst the best results available in the literature. The models are built up in accordance with OECD principles.

Halogen-specific total organic halogen analysis: Assessment by recovery of total bromine.

Determination of halogen-specific total organic halogen (TOX) is vital for studies of disinfection of waters containing bromide, since total organic bromine (TOBr) is likely to be more problematic than total organic chlorine. Here, we present further halogen-specific TOX method optimisation and validation, focusing on measurement of TOBr. The optimised halogen-specific TOX method was validated based on the recovery of model compounds covering different classes of disinfection by-products (haloacetic acids, haloacetonitriles, halophenols and halogenated benzenes) and the recovery of total bromine (mass balance of TOBr and bromide concentrations) during disinfection of waters containing dissolved organic matter and bromide. The validation of a halogen-specific TOX method based on the mass balance of total bromine has not previously been reported. Very good recoveries of organic halogen from all model compounds were obtained, indicating high or complete conversion of all organic halogen in the model compound solution through to halide in the absorber solution for ion chromatography analysis. The method was also successfully applied to monitor conversion of bromide to TOBr in a groundwater treatment plant. An excellent recovery (101%) of total bromine was observed from the raw water to the post-chlorination stage. Excellent recoveries of total bromine (92%-95%) were also obtained from chlorination of a synthetic water containing dissolved organic matter and bromide, demonstrating the validity of the halogen-specific TOX method for TOBr measurement. The halogen-specific TOX method is an important tool to monitor and better understand the formation of halogenated organic compounds, in particular brominated organic compounds, in drinking water systems.

Low-cost colorimetric assay of biothiols based on the photochemical reduction of silver halides and consumer electronic imaging devices.

This work describes a new approach for the determination of free biothiols in biological fluids that exploits some of the basic principles of early photographic chemistry - that was based on silver-halide recording materials - and uses broadly-available imaging devices (i.e. flatbed scanners) as detectors. Specifically, the proposed approach relies on the ability of biothiols to bind to silver ions and dissociate the silver halide crystals thus changing the photosensitivity of silver halide crystal suspension. The changes induced by biothiols on the light intensity transmitted through the silver halide suspension, after photochemical reduction, were measured with a simplified photometric approach that employs a flatbed scanner operating in transmittance mode. The overall analytical procedure for the determination of biothiols was easily executable, fast and could be applied with inexpensive and commercially available materials and reagents. What is more, physiologically relevant biothiol levels could be inspected even by the unattended eye. The developed assay was successfully applied to the determination of biothiols in urine and blood plasma samples with detection limits as low as 10µM, satisfactory recoveries (92-97%), good reproducibility (6.7-8.8%) and high selectivity against other major components of biological fluids. The utility of the method to the determination of reduced/oxidized thiol ratio's as well as its application under natural light illumination, without external energy sources, was also demonstrated and is discussed with regard to point-of need applications in facility-limited settings.

Pd-Metalated Conjugated Nanoporous Polycarbazoles for Additive-Free Cyanation of Aryl Halides: Boosting Catalytic Efficiency through Spatial Modulation.

Transition-metal-catalyzed cyanation of aryl halides is a common route to benzonitriles, which are integral to many industrial procedures. However, traditional homogeneous catalysts for such processes are expensive and suffer poor recyclability, so a heterogeneous analogue is highly desired. A novel spatial modulation approach has been developed to fabricate a heterogeneous Pd-metalated nanoporous polymer, which catalyzes the cyanation of aryl halides without need for ligands. The catalyst displays high activity in the synthesis of benzonitriles, including high product yields, excellent stability and recycling, and broad functional-group tolerance.

Grand Canonical Monte Carlo coupled multiscale simulation for electrochemical and solvent parameters of silver halide systems in water.

Grand Canonical Monte Carlo methods in conjunction with continuum Multiscale simulation to estimate the hydration energies and surface potentials of silver halides as demonstrated elsewhere is employed by incorporating random distribution of molecules, nearest neighbor distances and hydration numbers. The extent of dehydration during each step and the corresponding variation in the hydration numbers are evaluated, assuming the validity of hard spheres. These estimates are then employed to deduce the redox potential of the reaction viz. 2AgX(solution)⇔2Ag(solid)+X2(gas). The dependence of these values on the nature of the halides and solvation characteristics is indicated.

Antioxidant Activity of Marine Algal Polyphenolic Compounds: A Mechanistic Approach.

Polyphenolic compounds isolated from marine algae exhibit a broad spectrum of beneficial biological properties, including antioxidant, anticancer, antimicrobial, anti-inflammatory, and antidiabetic activities, along with several other bioactivities centered on their antioxidant properties. Consequently, polyphenolic compounds are increasingly being investigated for their potential use in food, cosmetic, and pharmaceutical applications. The antioxidant activities of these compounds have been explored widely through experimental studies. Nonetheless, a theoretical understanding of the structural and electronic properties could broaden research perspectives, leading to the identification and synthesis of efficient structural analogs with prophylactic uses. This review briefly summarizes the current state of knowledge regarding antioxidant polyphenolic compounds in marine algae with an attempt to describe the structure-activity relationship.

Assessment of the Halogen Content of Brazilian Inhalable Particulate Matter (PM10) Using High Resolution Molecular Absorption Spectrometry and Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry, with Direct Solid Sample Analysis.

Halogens in the atmosphere play an important role in climate change and also represent a potential health hazard. However, quantification of halogens is not a trivial task, and methods that require minimum sample preparation are interesting alternatives. Hence, the aim of this work was to evaluate the feasibility of direct solid sample analysis using high-resolution continuum source molecular absorption spectrometry (HR-CS MAS) for F determination and electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICP-MS) for simultaneous Cl, Br, and I determination in airborne inhalable particulate matter (PM10) collected in the metropolitan area of Aracaju, Sergipe, Brazil. Analysis using HR-CS MAS was accomplished by monitoring the CaF molecule, which was generated at high temperatures in the graphite furnace after the addition of Ca. Analysis using ETV-ICP-MS was carried out using Ca as chemical modifier/aerosol carrier in order to avoid losses of Cl, Br, and I during the pyrolysis step, with concomitant use of Pd as a permanent modifier. The direct analysis approach resulted in LODs that were proven adequate for halogen determination in PM10, using either standard addition calibration or calibration against a certified reference material. The method allowed the quantification of the halogens in 14 PM10 samples collected in a northeastern coastal city in Brazil. The results demonstrated variations of halogen content according to meteorological conditions, particularly related to rainfall, humidity, and sunlight irradiation.

[Removal of AOX in Activated Sludge of a Chemical Pharmaceutical Industry with Fenton Oxidation].

This study aimed to remove AOX (adsorbable organic halogens) with Fenton oxidation from activated sludge in a chemical pharmaceutical industry. The influences of H2O2 dosage, Fe2+ dosage and reaction time were investigated, based on which the reaction conditions for AOX removal were optimized, and the reaction mechanism was discussed. The optimized reaction conditions were as follows:0.90 mol·L-1 of H2O2, 0.045 mol·L-1 of Fe2+[n (Fe2+):n (H2O2) of 1:20] and reaction time of 2 h. Under the optimized conditions, 70.7% of AOX in the sludge and 78.5% of AOX in the supernatant were removed. GC-MS analysis revealed that eleven organic halides were detectable in the original sludge. After Fenton reaction, only three organic halides were detectable, and their peak areas were reduced by 40%-50%. Toxic and hazardous non-AOX organic matters such as xylene, diisobutyl phthalate were also effectively removed.

A Concise and Atom-Economical Suzuki-Miyaura Coupling Reaction Using Unactivated Trialkyl- and Triarylboranes with Aryl Halides.

A concise and atom-economical Suzuki-Miyaura coupling of trialkyl- and triarylboranes with aryl halides is described. This new protocol represents the first general, practical method that efficiently utilizes peralkyl and peraryl groups of the unactivated trialkyl- and triarylboranes for the Suzuki-Miyaura coupling reaction.

A cryospectroscopic infrared and Raman study of the CX⋯π halogen bonding motif: complexes of the CF3Cl, CF3Br, and CF3I with ethyne, propyne and 2-butyne.

Experimental information on the C-X⋯π halogen bonding motif was obtained by studying the formation of molecular complexes of CF3Cl, CF3Br and CF3I with ethyne, propyne and 2-butyne in liquid krypton, using FTIR and Raman spectroscopy. For CF3Br, experimental evidence was found for the formation of 1:1 complexes with propyne and 2-butyne only, while for CF3I spectroscopic features confirming the existence of the halogen bonded complexes were observed for ethyne, propyne and 2-butyne. In addition, at higher concentrations of CF3I and 2-butyne, weak absorptions due to a 2:1 complex were also observed. The experimental complexation enthalpies, obtained by using spectra recorded at temperatures between 120 K and 140 K, are -5.9(3) kJ mol(-1) for CF3I.ethyne, -5.6(3) kJ mol(-1) for CF3Br.propyne, -8.1(2) kJ mol(-1) for CF3I.propyne, -7.3(2) kJ mol(-1) for CF3Br.2-butyne, -10.9(2) kJ mol(-1) for CF3I.2-butyne and -20.9(7) kJ mol(-1) for (CF3I)2.2-butyne. The experimental study is supported by theoretical data obtained from ab initio calculations at the MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) levels, and Monte Carlo Free Energy Perturbation (MC-FEP) simulations. The experimental and theoretical values on the C-X⋯π halogen-bonding motifs studied are compared with previously reported data for the complexes with ethene and propene and with preliminary results obtained for benzene and toluene.