Microfluidic Device for the Determination of Water Chlorination Levels Combining a Fluorescent meso-Enamine Boron Dipyrromethene Probe and a Microhydrocyclone for Gas Bubble Separation.

Chlorination procedures are commonly applied in swimming pool water and wastewater treatment, yet also in food, pharmaceutical, and paper production. The amount of chlorine in water needs to be strictly controlled to ensure efficient killing of pathogens but avoid the induction of negative health effects. Miniaturized microfluidic fluorescence sensors are an appealing approach here when aiming at online or at-site measurements. Two meso-enamine-substituted boron dipyrromethene (BODIPY) dyes were found to exhibit favorable indication properties, their reaction with hypochlorite leading to strong fluorescence enhancement. Real-time assays became possible after integration of these fluorescent probes with designed two-dimensional (2D) and three-dimensional (3D) microfluidic chips, incorporating a passive sinusoidal mixer and a microhydrocyclone, respectively. A comparison of the two microfluidic systems, including their abilities to prevent accumulation or circulation of microbubbles produced by the chemical indication reaction, showed excellent fluidic behavior for the microhydrocyclone-based device. After coupling to a miniaturized optical reader for fluorescence detection, the 2D microfluidic system showed a promising detection range of 0.04-0.5 mg L-1 while still being prone to bubble-induced fluctuations and suffering from considerably low signal gain. The microhydrocyclone-based system was distinctly more robust against gas bubbles, showed a higher signal gain, and allowed us to halve the limit of detection to 0.02 mg L-1. The use of the 3D system to quantify the chlorine content of swimming pool water samples for sensitive and quantitative chlorine monitoring was demonstrated.

New ISE-Based Apparatus for Na+, K+, Cl-, pH and Transepithelial Potential Difference Real-Time Simultaneous Measurements of Ion Transport across Epithelial Cells Monolayer⁻Advantages and Pitfalls.

Cystic Fibrosis (CF) is the most common fatal human genetic disease, which is caused by a defect in an anion channel protein (CFTR) that affects ion and water transport across the epithelium. We devised an apparatus to enable the measurement of concentration changes of sodium, potassium, chloride, pH, and transepithelial potential difference by means of ion-selective electrodes that were placed on both sides of a 16HBE14σ human bronchial epithelial cell line that was grown on a porous support. Using flat miniaturized ISE electrodes allows for reducing the medium volume adjacent to cells to approximately 20 µL and detecting changes in ion concentrations that are caused by transport through the cell layer. In contrast to classic electrochemical measurements, in our experiments neither the calibration of electrodes nor the interpretation of results is simple. The calibration solutions might affect cell physiology, the medium composition might change the direction of actions of the membrane channels and transporters, and water flow that might trigger or cut off the transport pathways accompanies the transport of ions. We found that there is an electroneutral transport of sodium chloride in both directions of the cell monolayer in the isosmotic transepithelial concentration gradient of sodium or chloride ions. The ions and water are transported as an isosmotic solution of 145 mM of NaCl.

Emission of submicron aerosol particles in cement kilns: Total concentration and size distribution.

Cement plants are responsible for particle and gaseous emissions into the atmosphere. With respect to particle emission, the greater part of is in the range from 0.05 to 5.0 µm in diameter. In the last years attention was paid to submicron particles, but there is a lack of available data on the emission from stationary sources. In this paper, concentration and size distribution of particles emitted from four cement kilns, in relationship to operational conditions (especially the use of alternative fuel to coal) of the clinker process are reported. Experimental campaigns were carried out by measuring particles concentration and size distribution at the stack of four cement plants through condensation particle counter (CPC) and scanning mobility particle sizer spectrometer (SMPS). Average total particle number concentrations were between 2000 and 4000 particles/cm³, about 8-10 times lower that those found in the corresponding surrounding areas. As for size distribution, for all the investigated plants it is stable with a unimodal distribution (120-150 nm), independent from the fuel used.

Removal of As(V), Cr(III) and Cr(VI) from aqueous environments by poly(acrylonitril-co-acrylamidopropyl-trimethyl ammonium chloride)-based hydrogels.

Cationic poly(Acrylonitril-co-Acrylamidopropyl-trimethyl Ammonium Chloride) (p(AN-co-APTMACl)) hydrogels in bulk were synthesized by using acrylonitrile (AN) and 3-acrylamidopropyl-trimethyl ammonium chloride (APTMACl) as monomers. The prepared hydrogels were exposed to amidoximation reaction to replace hydrophobic nitrile groups with hydrophilic amidoxime groups that have metal ion binding ability. Those replacements were increased the hydrogels absorption capacity for As(V) and Cr(VI). Langmuir and Freundlich isotherms equations were utilized to obtain the best-fitted isotherm model for the absorption of the ions at different metal ion concentrations. The absorption data of As(V) ion were fitted well to Freundlich isotherm while those of Cr(VI) and Cr(III) ions were fitted well to Langmuir isotherm. The maximum absorption of poly(3-acrylamidopropyl-trimethyl ammonium chloride (p(APTMACl)) and amid-p(AN-co-APTMACl) macro gels were 22.39 mg and 21.83 mg for As(V), and 30.65 mg and 18.16 mg for Cr(VI) ion per unit gram dried gel, respectively. Kinetically, the absorption behaviors of Cr(III) and Cr(VI) ions were fitted well to a pseudo 2nd-order kinetic model and those of As(V) ions were fitted well to a pseudo 1st order kinetic model.

Adsorption characteristics of bio-adsorbent on chromium(III) in industrial wastewater.

The removal of chromium(III) (Cr(III)) from industrial wastewater by various low-cost methods has been widely investigated. In this paper, a type of bio-adsorbent was prepared using rice straw modified by fermentation and simple chemical treatment. The aim is to detect the adsorption mechanism and characteristics on Cr(III) ions. The analysis shows that the bio-adsorbent possesses four modified characteristics for Cr(III) adsorption. The first one is the acquired physical adsorption involving concave and convex structures. The second one is the effects of the hydrogen bonding surface hydroxyl groups and the metal chromium ion with complexation. The third one is mainly caused by hydrophilic active groups that possess carboxyl and hydroxyl groups during microbial degradation to combine with ions. The final one is the bio-adsorbent had high adsorption for low concentration of Cr(III) ions. The highest removal of around 97.45% was obtained at pH 5.0, bio-adsorption dosage of 0.5 g L(-1), and initial Cr(III) concentration of 20 mg L(-1). The adsorption process followed the pseudo second-order model (R(2) > 0.99), while the isotherms were fitted to the Freundlich equation (68.1926 mg g(-1)), mainly by chemical adsorption. This study demonstrates the potential of using this biosorbent to remove Cr(III) from both synthetic and industrial wastewater.

Determination of lewisite constituents in aqueous samples using hollow-fibre liquid-phase microextraction followed by gas chromatography-mass spectrometry.

The applicability of hollow-fibre liquid-phase microextraction for extracting 2-chlorovinyldichloroarsine (lewisite 1), bis(2-chlorovinyl)chloroarsine (lewisite 2), tris(2-chlorovinyl)arsine (lewisite 3) and arsenic trichloride from aqueous samples is reported. Parameters affecting the extraction efficiency of these chemicals were optimised. These parameters included the type of derivatising agent, extraction solvent, derivatisation method, pH, ionic strength, stirring speed and extraction time. A linear range between 0.002 and 0.2 µg/mL was established for the lewisites with good square regression coefficients (0.9955-0.9992). Good reproducibility with relative standard deviations (RSDs) from 8 to 10% was achieved. The limit of detection was 0.002 µg/mL for the lewisites and 0.005 µg/mL for arsenic trichloride (3:1 signal-to-noise ratio). The extraction method was validated with a proficiency test sample issued by the Organisation for the Prohibition of Chemical Weapons (OPCW). The rapidity and precision of the new method should help deter against the employment of lewisite as a chemical warfare agent: its use could be confirmed easily from analysis of aqueous samples.

The simultaneous removal of calcium, magnesium and chloride ions from industrial wastewater using magnesium-aluminum oxide.

In this article, a method for simultaneous removal of calcium, magnesium and chloride by using Mg0.80Al0.20O1.10 as a Magnesium-Aluminum oxide (Mg‒Al oxide) was investigated. Mg‒Al oxide obtained by thermal decomposition of the Mg-Al layered double hydroxide (Mg-Al LDH). The synthesized Mg‒Al oxide were characterized with respect to nitrogen physicosorption, X-ray diffraction (XRD) and field emission scan electron microscopy (FESEM) morphology. Due to high anion-exchange capacity of Mg‒Al oxide, it was employed in simultaneously removal of Cl(-), Mg(+2) and Ca(+2) from distiller waste of a sodium carbonate production factory. For this purpose, experiments were designed to evaluate the effects of quantity of Mg‒Al oxide, temperature and time on the removal process. The removal of Cl(-), Mg(+2) and Ca(+2) from wastewater was found 93.9%, 93.74% and 93.25% at 60°C after 0.5 h, respectively. Results showed that the removal of Cl(-), Mg(+2) and Ca(+2) by Mg‒Al oxide increased with increasing temperature, time and Mg‒Al oxide quantity.

Removal of chloride from fly ash produced in hazardous waste incineration by leaching and displacement washing in a vertical filter press.

Fly ash is generated in large quantities by waste incineration processes. Chloride is commonly present in the fly ash produced by the incineration of hazardous materials, such as polyvinylchloride plastic. Major difficulties related to the disposal and handling of fly ash include the high concentration of easily leachable chlorides, heavy metals and toxic compounds. In order to avoid adverse environmental effects from the disposal of fly ash, the content of soluble chlorides must be reduced. One of the most effective options for chloride removal is leaching and displacement washing in a filter press. The primary aim of this study was to obtain efficient removal of chloride from fly ash by utilizing a leaching and displacement washing process, carried out in a filter press. The secondary objective was to obtain high filtration capacities and low filter cake moisture contents. The slurry was prepared by mixing fly ash with water at an ash:water ratio of 1:2 and filtered to separate the solids from the liquid. After solid-liquid separation, most of the dissolved residual chloride was removed from the filter cake by washing the cake with fresh water in the second stage of separation. It was possible to remove up to 98% of the total chloride and to obtain sufficient filtration capacities. The residual moisture content of the filter cakes varied from 22 to 35 wt%, which meant that the cakes could be disposed of in landfill, or possibly utilized as a construction material.

Thermodynamic modeling of Cl(-), NO3(-) and SO4(2-) removal by an anion exchange resin and comparison with Dubinin-Astakhov isotherms.

The removal of chloride, nitrate, and sulfate ions from wastewaters by a macroporous ion-exchange resin is studied through the experimental results obtained for six ion exchange systems, OH(-)/Cl(-), OH(-)/NO3(-), OH(-)/SO4(2-), and HCO3(-)/Cl(-), Cl(-)/NO3(-), Cl(-)/SO4(2-). The results are described through thermodynamic modeling, considering either an ideal or a nonideal behavior of the ionic species in the liquid and solid phases. The nonidealities are determined by the Davies equation and Wilson equations in the liquid and solid phases, respectively. The results show that the resin has a strong affinity for all the target ions, and the order of affinity obtained is OH(-) < HCO3(-) < Cl(-) < NO3(-) < SO4(2-). The calculation of the changes in standard Gibbs free energies (ΔG(0)) shows that even though HCO3(-) has a lower affinity to the resin, it may affect the removal of Cl(-), and in the same way that Cl(-) may affect the removal of NO3(-) and SO4(2-). The application of nonidealities in the thermodynamic model leads to an improved fit of the model to the experimental data with average relative deviations below 1.5% except for the OH(-)/SO4(2-) system. On the other hand, considering ideal or nonideal behaviors has no significant impact on the determination of the selectivity coefficients. The thermodynamic modeling is also compared with the Dubinin-Astakhov adsorption isotherms obtained for the same ion exchange systems. Surprisingly, the latter performs significantly better than the ideal thermodynamic model and nearly as well as the nonideal thermodynamic model.

Centralized softening as a solution to chloride pollution: An empirical analysis based on Minnesota cities.

Chloride is a key component of salt, used in many activities such as alkali production, water treatment, and de-icing. Chloride entering surface and groundwater is a concern due to its toxicity to aquatic life and potential to degrade drinking water sources. Minnesota being a hard-water state, has a high demand for water softening. Recent research has found that home-based water softeners contribute significantly to chloride loading at municipal wastewater treatment plants (WWTPs). Because of this, many WWTPs would now require water quality based effluent limits (WQBELs) to comply with the state's chloride water quality standards (WQS), unless they install chloride treatment technologies, which are limited and cost-prohibitive to most communities. A potential solution to this problem, is shifting from home-based water softening to a system where water is softened at drinking water plants, before reaching homes, i.e. centralized softening, analyzed in this paper based on its ability to address both chloride pollution and water softening needs, at reasonable cost. We estimate lifetime costs of three alternative solutions: centralized softening, home-based softening, and a Business as Usual (BAU) or baseline alternative, using annualized 20-year loan payments and Net Present Value (NPV), applied to 84 Minnesota cities with matching data on drinking water plants and WWTPs. We find that centralized softening using either Reverse Osmosis (RO) or lime-softening technologies is the more cost-effective solution, compared to the alternative of home-based softening with end-of-pipe chloride treatment, with a cost ratio in the range 1:3-1:4. Between the two centralized softening options, we find RO-softening to be the lower cost option, only slightly more costly (1.1 cost ratio) than the BAU option. Considering additional environmental and public health benefits, and cost savings associated with removal of home-based softeners, our results provide helpful information to multiple stakeholders interested in an effective solution to chloride pollution.

Study on the effects of chloride depletion on photosystem II using different chloride depletion methods.

Chloride is an indispensable factor for the functioning of oxygen evolving complex (OEC) and has protective and activating effects on photosystem II. In this study we have investigated mainly by EPR, the properties of chloride-sufficient, chloride-deficient and chloride-depleted thylakoid membranes and photosystem II enriched membranes from spinach. The results on the effects of different chloride depletion methods on the structural and functional aspects of photosystem II showed that chloride-depletion by treating PS II membranes with high pH is a relatively harsh way causing a significant and irreparable damage to the PS II donor side. Damage to the acceptor side of PS II was recovered almost fully in chloride-deficient as well as chloride-depleted PS II membranes.

Electrochemical disinfection of secondary wastewater treatment plant (WWTP) effluent.

In this work the electrochemical disinfection of the effluent of a secondary wastewater treatment plant is investigated. In the experimental work, performed on-site with real effluents of the WWTP located in Vuelta Ostrera (Cantabria, Spain), boron-doped diamond (BDD) electrodes were employed. The initial concentration of E. coli in the effluent of the WWTP varied in the range 1.3 x 104-5.2 x 105 cfu/mL. The influence of two operation variables on the kinetics of E. coli deactivation was investigated: i) The applied current density was varied in the range J=40-120 mA/cm², showing first order kinetics, and linear dependency of the apparent kinetic constant with the applied current density; and ii) the chloride concentration was varied in the range 60-1,050 mg/L, showing that increasing chloride content also enhanced the kinetics of the E. coli deactivation. The latter parameter is particularly important in coastal areas, as in the case of the present study. The formation of disinfection by-products (DBPs) was followed by measuring the content of trihalomethanes (THMs) that nevertheless was maintained below 100 µg/L, so it can be concluded that the formation of DBPs is not a disadvantage of electrochemical disinfection of secondary effluents of WWTP.

Degradation of a mixture of pollutants in water using the UV/H2O2 process.

The degradation reaction of a simple mixture of pollutants (dichloroacetic acid + formic acid) employing H2O2 and UVC radiation (253.7 nm) has been studied in a well-mixed reactor which operates inside a recycling system. The aim of this work is to develop a systematic methodology for treating degradation of mixtures of pollutants, starting from a rather manageable system to more complex aggregates. In this contribution, the effects of different variables such as hydrogen peroxide/pollutant mixture initial concentration ratio, pH and incident radiation at the reactor wall were studied. The results show that the best degrading conditions are: pH = 3.5 and hydrogen peroxide concentrations from 3.9 to 11.8 mM (134-400 mg/L), for initial concentrations of 1.10 and 0.39 mM for formic acid and dichoroacetic acid respectively (50 mg/L for both pollutants). The influence of the incident radiation at the reactor wall on the degradation rates of the mixture is significant. In addition to this, it has been shown that in the employed aqueous solution no stable reaction intermediates are formed. On this basis, a complete reaction scheme for the mixture is proposed that is suitable for a reaction kinetics mathematical modeling of the mixture and further studies of increasing complexity.

A novel method for salts removal from municipal solid waste incineration fly ash through the molten salt thermal treatment.

The disposal of the hazardous municipal solid waste (MSW) incineration fly ash is a critical environmental issue in China and the high contents of salts in the fly ash make the ash disposal extremely difficult. The present study proposes a novel method for the salts removal from MSW incineration fly ash using molten carbonates and chlorides at moderate temperatures from 773 K to 1073 K. The results showed that molten salts could effectively extract alkali and alkaline earth metals chlorides and sulfates from the fly ash. Other ash components, like Si/Al-compounds, were precipitated from the molten salts and concentrated in residues. By comparison, molten carbonates showed greater capability in the salts extraction while molten chlorides showed better selectivity in chlorides removal from MSW incineration fly ash. These findings suggest that the optimization of molten salts system could further prove the potential applicability of molten salts thermal treatment method for the salts removal from MSW incineration fly ash.

The Dynamic Response of Sweat Chloride to Changes in Exercise Load Measured by a Wearable Sweat Sensor.

Wearable sensors enable the monitoring of an individual's sweat composition in real time. In this work, we recorded real-time sweat chloride concentration for 12 healthy subjects in three different protocols involving step changes in exercise load and compared the results to laboratory-based analysis. The sensor results reflected the changes in exercise load in real time. On increasing the exercise load from 100 W to 200 W the sweat chloride concentration increased from 12.0 ± 5.9 to 31.4 ± 16 mM (mean ± SD). On decreasing the load from 200 W to 100 W, the sweat chloride concentration decreased from 27.7 ± 10.5 to 14.8 ± 8.1 mM. The half-time associated with the change in sweat chloride, defined as the time at which the concentration reached half of the overall change, was about 6 minutes. While the changes in sweat chloride were statistically significant, there was no correlation with changes in sweat rate or other physiological parameters, which we attribute to intra-individual variation (SD = 1.6-8.1 mM). The response to exercise-induced sweating was significantly different to chemically-induced sweating where the sweat chloride concentration was almost independent of sweat rate. We speculate that this difference is related to changes in the open probability of the CFTR channel during exercise, resulting in a decrease in reabsorption efficiency at higher sweat rates.

Identification of most preferable reaction pathways for chloride depletion from size segregated sea-salt aerosols: A study over high altitude Himalaya, tropical urban metropolis and tropical coastal mangrove forest in eastern India.

Depletion of chloride from sea-salt aerosols affects their hygroscopicity, cloud condensation nuclei activity as well as microphysical and chemical properties of aerosols and clouds modifying earth-atmosphere radiative balance. Here, we proposed five possible reaction pathways through which the inorganic acids (H2SO4 and HNO3) could deplete chloride from sea-salt aerosols. We determined "maximum potential contribution" (MPC) of each acid and compared the MPC with actual chloride depletion. This step-by-step approach enables us to identify the most preferable reaction pathway(s) for coarse, superfine, accumulation and ultrafine aerosols over a Himalayan station (Darjeeling), a tropical urban station (Kolkata) and a tropical mangrove forest at the north-east coast of Bay of Bengal (Sundarban) in India. Over Kolkata and Darjeeling, locally generated acids reacted with transported sea-salts. Over Sundarban, the locally generated sea-salts from the Bay of Bengal reacted with the acids of biomass burning plume transported from Eastern Ghat and continental haze transported from upper Indo-Gangetic Plain. The average chloride depletion in PM10 ranged between 70 and 74% over Sundarban and 31-34% over Kolkata and Darjeeling. We observed that HNO3(g) depleted the larger (>1 µm) chlorides whereas H2SO4(g) depleted the smaller (<1 µm) chlorides over Kolkata and Darjeeling. However, in addition to H2SO4(g) and HNO3(g), some other species could be involved in chloride depletion over Sundarban mainly during winter. The study reveals that Sundarban acts as the major sink of the inorganic acids transported from Eastern Ghat biomass burning plume inhibiting their further advection towards inland regions.

Reconstitution and phosphorylation of chloride channels from airway epithelium membranes.

Airway epithelial chloride secretion is controlled by the apical-membrane chloride permeability. Purified apical-membrane vesicles from bovine tracheal epithelium have now been shown to contain functional chloride channels by using the planar-bilayer technique. Three types of chloride channels were observed; a voltage-dependent, calcium-independent, 71-picoSiemen (in 150 mM NaCl) channel accounted for more than 80 percent of the vesicular chloride conductance and was under strict control of phosphorylation. The channel underwent a fast rundown in less than 2 to 3 minutes of recording, and reactivation required in situ exposure to a phosphorylating "cocktail" containing the catalytic subunit of the adenosine 3',5'-monophosphate (cAMP)-dependent protein kinase. Mean open time and open probability were increased after phosphorylation, whereas slope conductance remained unchanged. Thus, metabolic control of tracheal chloride single channels can now be studied in vitro.

Purification and reconstitution of chloride channels from kidney and trachea.

Chloride channels mediate absorption and secretion of fluid in epithelia, and the regulation of these channels is now known to be defective in cystic fibrosis. Indanyl-oxyacetic acid 94 (IAA-94) is a high-affinity ligand for the chloride channel, and an affinity resin based on that structure was developed. Solubilized proteins from kidney and trachea membranes were applied to the affinity matrix, and four proteins with apparent molecular masses of 97, 64, 40, and 27 kilodaltons were eluted from the column by excess IAA-94. A potential-dependent 36Cl- uptake was observed after reconstituting these proteins into liposomes. Three types of chloride channels with single-channel conductances of 26, 100, and 400 picosiemens were observed after fusion of these liposomes with planar lipid bilayers. Similar types of chloride channels have been observed in epithelia.

Concerted dismutation of chlorite ion: water-soluble iron-porphyrins as first generation model complexes for chlorite dismutase.

Three iron-5,10,15,20-tetraarylporphyrins (Fe(Por-Ar4), Ar = 2,3,5,6-tetrafluro-N,N,N-trimethylanilinium (1), N,N,N-trimethylanilinium (2), and p-sulfonatophenyl (3)) have been investigated as catalysts for the dismutation of chlorite (ClO2-). Degradation of ClO2- by these catalysts occurs by two concurrent pathways. One leads to formation of chlorate (ClO3-) and chloride (Cl-), which is determined to be catalyzed by O=FeIV(Por) (Compound II) based on stopped-flow absorption spectroscopy, competition with 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonicacid), 18O-labeling studies, and kinetics. The second pathway is a concerted dismutation of chlorite to dioxygen (O2) and chloride. On the basis of isotope labeling studies using a residual gas analyzer, the mechanism is determined to be formation of O=FeIV(Por)*+ (Compound I) from oxygen atom transfer, and subsequent rebound with the resulting hypochlorite ion (ClO-) to give dioxygen and chloride. While the chlorate production pathway is dominant for catalysts 2 and 3, the O2-producing pathway is significant for catalyst 1. In addition to chlorite dismutation, complex 1 catalyzes hypochlorite disproportionation to chloride and dioxygen quantitatively.

A comparison of pilot-scale photocatalysis and enhanced coagulation for disinfection byproduct mitigation.

This study evaluated pilot-scale photocatalysis and enhanced coagulation for their ability to remove or destroy disinfection byproduct (DBP) precursors, trihalomethane (THM) formation potential (FP), and THMs in two Arizona surface waters. Limited photocatalysis (<5 kWh/m(3)) achieved reductions in most of the DBP precursor parameters (e.g., DOC, UV(254), and bromide) but led to increased chlorine demand and THMFP. In contrast, enhanced coagulation achieved reductions in the DBP precursors and THMFP. Extended photocatalysis (<320 kWh/m(3)) decreased THMFP once the energy consumption exceeded 20 kWh/m(3). The photocatalytic energy requirements for THM destruction were considerably lower (EEO=20-60 kWh/m(3)) than when focusing on precursor destruction and THMFP. However, rechlorination increased the total THM (TTHM) concentration well beyond the raw value, thereby negating the energy benefits of this application. Enhanced coagulation achieved consistent 20-30% removals of preformed THMs. Outstanding issues need to be addressed before TiO(2) photocatalysis is considered feasible for DBP mitigation; traditional strategies, including enhanced coagulation, may be more appropriate.