Determination Of Chlorine Research Articles

Indirect determination of free chlorine in seawater by cyclic voltammetry using graphite–epoxy composite electrode: Hydrogen adsorption capacity of graphite–epoxy composite is one–third of that of platinum

A new possibility of indirect determination of free chlorine using a graphite–epoxy composite(GEC) electrode instead of Pt disk electrode was suggested by interpreting the relationship between the peak current of the oxidation peak for hydrogen generated through water electrolysis in CV and the amount of the free chlorine. The linear response range of concentration was 0.06–0.2 mg∙L−1 with correlation coefficient of 0.9951 (n = 5) and the sensitivity of 1225 μA cm−2 mg−1 L. The limit of detection (LOD) calculated from the 3σ IUPAC criteria was 1.2 × 10−2 mg L−1. The relative standard deviation (RSD) to 0.06 mg L−1 was 4.65 %(n = 10). The results show that the amount of free chlorine in the disinfected seawater can be indirectly determined by using a GEC electrode without influence of interferences unlike a Pt disk electrode. On the other hand, in this paper, a new method is proposed to evaluate the relative hydrogen adsorption capacity by the sensitivity of GEC electrode compared with that of Pt disk electrode. During the investigation of the hydrogen adsorption on the surface of the working electrode, we obtained the result that the hydrogen adsorption capacity of GEC is one-third of that of platinum.

Determination of Chlorine and Fluorine in Teas by Ion Chromatography after Pyrohydrolysis Sample Preparation Optimized by Box-Behnken Design

Determination of Chlorine and Fluorine in Teas by Ion Chromatography after Pyrohydrolysis Sample Preparation Optimized by Box-Behnken Design

Determination of sodium, chlorine, and bromine concentrations in breast milk using neutron activation: Correlation, regression, and machine learning predictions

Breast milk plays a vital role in infant health, providing essential nutrients that directly impact nutrition and development. Understanding its elemental composition, as well as the relationships among these elements, is crucial for assessing its nutritional adequacy. This study focused on determining the concentrations of sodium (Na), chlorine (Cl), and bromine (Br) in the breast milk of lactating mothers in Tehran, Iran, during early lactation. The primary objectives were to analyze the concentrations of these elements, investigate their interrelationships, and employ machine-learning techniques to predict their concentrations in breast milk. Neutron activation analysis (NAA) was used to precisely measure the levels of Na, Cl, and Br, while statistical methods, including correlation and regression analyses, were applied to further explore these relationships. Machine-learning models, specifically Random Forest and Linear Regression, were utilized to predict the concentrations of these elements based on their interdependencies. The study revealed mean concentrations of 5.12 mg/g for Na, 8.14 mg/g for Cl, and 11.84 mg/kg for Br in the breast milk samples. A strong positive correlation was observed between Na and Cl (r = 0.976, p < 0.001), while moderate positive correlations were found between Na and Br (r = 0.558, p < 0.001) and Cl and Br (r = 0.606, p < 0.001). Multiple regression models showed that 94.7 % of the variance in Na concentration could be explained by Cl and Br levels (R-squared = 0.947), with a strong positive association between Cl and Na, and a slight inverse relationship between Br and Na. A similar model for Cl concentrations showed strong predictive power, with Na being a significant predictor. However, the model for Br concentrations explained a smaller proportion of variance (R-squared = 0.318), suggesting that additional factors influencing Br levels were not captured in this study. Furthermore, multicollinearity was observed between Na and Cl (VIF = 20.675), indicating potential interactions between these elements. This study highlights the significant correlations between Na, Cl, and Br in breast milk, with particularly strong predictive models for Na and Cl concentrations. The findings also suggest the need for further investigation into the factors affecting Br concentrations. Overall, this research provides valuable insights into the elemental composition of breast milk and its implications for infant nutrition and health.

A fast and sensitive colorimetric sensor for residual chlorine detection made with oxidized cellulose

Residual chlorine from widespread disinfection processes forms byproducts in water that are harmful to humans and ecosystems. Portable sensors are essential tools for the on-site monitoring of residual chlorine in environmental samples. Here, an inexpensive colorimetric sensor was developed by grafting via amidation the chromogen orthotolidine (OTO) to the surface of a TEMPO-oxidized cellulose filter paper (O-TOFP). A thorough characterization of the sensor strip demonstrated that it was highly stable and that it could be stored for a long period before usage. O-TOFP had a fast response time of 30 s, was highly selective for residual chlorine ions (ClO−) with an accuracy of at least 95 %, and exhibited an excellent limit of detection of only 0.045 mg/L when combined with smartphone image acquisition. With its many positive features, the easy-to-use and robust O-TOFP sensor described here could become a useful tool for the determination of residual chlorine in different water samples.

Method development for multielement determination of halogens and sulfur in teas

Abstract Microwave-induced combustion was evaluated as a sample preparation method for several types of tea (black, green, lemon balm, boldo, and mint) for further determination of bromine, chlorine, fluorine, iodine, and sulfur by ion chromatography. Parameters such as the sample mass efficiently decomposed and the most suitable absorbing solution (ultrapure water and 25, 50, 100, and 150 mmol L−1 NH4OH) were evaluated, considering the characteristics of the analytes and the determination technique used. The maximum sample mass possible to be decomposed was 900 mg of milled tea in the form of pellets, and the absorbing solution chosen was 100 mmol L−1 NH4OH, which provided suitable stabilization of the analytes (recoveries between 95 % and 103 %). To assess the accuracy of the proposed method, a certified reference material (BCR 060, aquatic plant) was analyzed. Agreements with the certified values ranged from 101 % to 107 %. The proposed method was used to analyze tea samples and the concentrations ranged from 549 to 2,549 mg kg−1 for chlorine, 223 to 828 mg kg−1 for fluorine, and 786 to 4,023 mg kg−1 for sulfur; bromine and iodine concentrations were below the limits of quantification (42 and 80 mg kg−1, respectively) in all evaluated samples.

Influence of Feedstock Particle Size on the Certain Determination of Chlorine and Bromine in Pyrolysis Oils from Waste Electrical and Electronic Equipment Plastics.

Rejected streams emerging from waste sorting and recycling plants are still capable of being valorized by unconventional recycling routes. This is the case of the plastic-rich fraction generated after the treatment of waste electrical and electronic equipment (WEEE). However, the material complexity of this stream supposes a handicap when it comes to obtaining repetitive results in laboratory-scale recycling processes. This work aims to highlight the influence that the pretreatment (mainly particle size reduction) of a real WEEE plastic-rich stream has on the variability of the concentration of halogens (representative pollutants) in the oils obtained from its recycling via pyrolysis. The pretreatment steps were based on the standards of the European Committee for Standardization (ECN) for the analysis of waste samples. Four samples were studied: the WEEE plastics as received; two milled samples (2 and 1 mm particle size) derived from the original one; and a simulated sample composed of virgin polymers. All the samples were treated under the same conditions: 500 °C reaction temperature, 15 °C min-1 heating rate, 30 min dwell time, and a 1 L min-1 nitrogen purge flow. The oils obtained in, at least, two pyrolysis tests performed on the same sample were deeply characterized, and the results were compared. The oils derived from the "as-received" sample showed an unacceptable relative standard deviation (RSD, ∼42%) in the chlorine concentration. The sample milled to 2 mm reduced the RSD on the concentration of chlorine in the oils down to 8%, while no enhancement in the results was observed for the further milled sample. The other two major pyrolysis fractions were also characterized, showing an overall enhancement in the RSD of the analysis of the main components of the gases, while no improvement in the solids pollutants' characterization was achieved.

Indirect determination of free chlorine in seawater by cyclic voltammetry using graphite–epoxy composite electrode: Hydrogen adsorption capacity of graphite–epoxy composite is one–third of that of platinum

A new possibility of indirect determination of free chlorine using a graphite–epoxy composite(GEC) electrode instead of Pt disk electrode was suggested by interpreting the relationship between the peak current of the oxidation peak for hydrogen generated through water electrolysis in CV and the amount of the free chlorine. The linear response range of concentration was 0.06–0.2 mg∙L−1 with correlation coefficient of 0.9951 (n = 5) and the sensitivity of 1225 μA cm−2 mg−1 L. The limit of detection (LOD) calculated from the 3σ IUPAC criteria was 1.2 × 10−2 mg L−1. The relative standard deviation (RSD) to 0.06 mg L−1 was 4.65%(n = 10). The results show that the amount of free chlorine in the disinfected seawater can be indirectly determined by using a GEC electrode without influence of interferences unlike a Pt disk electrode. On the other hand, in this paper, a new method is proposed to evaluate the relative hydrogen adsorption capacity by the sensitivity of GEC electrode compared with that of Pt disk electrode. During the investigation of the hydrogen adsorption on the surface of the working electrode, we obtained the result that the hydrogen adsorption capacity of GEC is one-third of that of platinum.

Enhanced ammonia oxidation by a photoelectrocatalysis‑chlorine system: The role of ClO• and free chlorine

The decomposition of ammonia-N to environmental-friendly N2 remains a fundamental problem for water treatment. We proposed a way to selectively and efficiently oxidize ammonia to N2 through an integrated photoeletrocatalysis‑chlorine reactions (PECCl) system based on a bifunctional TiO2 nanotube photoanode. The ·OH and HClO can be simultaneously generated on the TiO2 nanotube photoanode in this system, which can in situ form ClO· for efficient ammonia removal. Compared with electrochemical‑chlorine (EC-Cl), photocatalysis‑chlorine (PC-Cl) and photoelectrocatalysis (PEC) systems, the PEC-Cl system exhibited much higher electrocatalytic activity due to the synergetic effect of photoelectrocatalyst and electrocatalyst in bifunctional TiO2 nanotube electrode. The removal efficiency of ammonia-N and total-N reached 100.0 % and 93.3 % at 0.3 V (vs Ag/AgCl) in the PEC-Cl system. Moreover, the system was efficient under various pH conditions. The reactions between ClO−/ClO· and the N-containing intermediates contributed to the high performance of the system, which expanded the reactions from the electrode surface to the electrolyte. Furthermore, radical scavenging and free chlorine determination experiments confirmed that ClO· and free chlorine were the main active species that enabled the ammonia oxidation. This study presents new understanding on the role of active species for ammonia removal in wastewater.

Determination of chlorine in Passaic river water in New Jersey Newark area by titration method

Much of the lower river suffered severe pollution during the 19th and 20th centuries because of industrial waste discharges and improper waste disposal practices on adjacent land. All drinking water, both tap and bottled, includes surface sources such as rivers, stream lakes, and reservoirs, and ground water source (wells) may be containing small amounts of some contaminants. New Jersey’s Passaic River has been a heavily polluted industrial waterway, for more than a country. In this study, chlorine analysis has been done by EPA Titration method. In Passaic River above Newark, New Jersey, the chlorine result has been found to be 7.00 mg/mL (ppm). In wastewater the chlorine discharge limit range is between 3 mg/L and 200 mg/L, depending on the season, and the industrial area.

Novel method for chlorine determination in biofuel lipid feedstock by coupling a total sample introduction system (hTISIS) to an inductively coupled plasma tandem mass spectrometry (ICP-MS/MS)

BackgroundChlorine concentrations above 1 mg kg−1 in lipid feedstocks for biofuel production can generate corrosion issues in the different refining units as well as catalyst deactivation by clogging or fouling. To reach accurate analyses by inductively coupled plasma (ICP) techniques at low concentration levels, dilution in organic solvents rises as a simpler and more straightforward sample preparation methodology than conventional sample decomposition procedures (e.g., microwave-assisted acid digestion). However, matrix effects and the impact of the Cl chemical form on the signal must be overcome to obtain accurate results. ResultsIn this work, the high temperature torch integrated sample introduction system (hTISIS) operated at 350 °C is coupled to an inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) for the determination of Cl in lipid biofuel feedstock samples diluted in xylene and these results are compared with those reported by a conventional sample introduction system. Under optimal conditions of the hTISIS-ICP-MS/MS configuration, matrix effects are efficiently overcome (recovery values ranged from 101 to 104%) as well as the effect of the Cl chemical form on the signal for 6 organochloride compounds. Thus, an external calibration approach can be set to carry out the quantification of this element in real samples. The method is successfully validated, obtaining a good agreement in the Cl concentration reported in a standard reference material (SRM NIST 1634c) and also by comparing the concentration results obtained by external calibration and standard addition approaches in two biofuel feedstock samples. Significance and noveltyThe hTISIS coupled to an ICP-MS/MS system is used for the first time to overcome not only matrix effects but also the impact of the Cl chemical form in biofuel feedstock samples. This novel method, with a limit of quantification (LOQ) of 7.1 μg kg−1, give access to an accurate Cl determination in all kind of lipid feedstocks for clean fuel production.

Novel ultra-sensitive and highly selective cyanine sensors based on solvent-free microwave synthesis for the detection of trace hypochlorite ions in drinking water

The adoption of chlorine in drinking water disinfection with the determination of residual chlorine in the form of hypochlorite ion (ClO-) is in widespread demand. Several sensors including colorimetric, fluorometric, and electrochemical methods are currently in use, but detection limits and ease of application remain a challenge. In this work, two new cyanine derivatives-based ClO- sensors, that were prepared by solvent-free microwave synthesis, are reported. The two sensors are highly sensitive and selective to ClO-, exhibiting a noticeable color change visible to the naked eye. Additionally, the sensors can detect ClO- without interference from other potential water pollutants, with low detection limits of 7.43 ppb and 0.917 ppb based on absorption performance. When using fluorometric methods, the sensors' detection limits are pushed down to 0.025 ppb and 0.598 ppb for sensors I and II, respectively. The sensors can be loaded with paper strips for field and domestic detection of ClO- in tap water treatment installations. Using the quartz crystal microbalance (QCM) technique, these sensors showed strong detection sensitivity to ClO-, with detection limits of 0.256 ppm and 0.09 ppm for sensors I and II, respectively. Quantum chemical studies using density functional theory (DFT) calculations, natural bond orbital (NBO) analysis, molecular electrostatic potential (MESP), and time-dependent density functional theory (TD-DFT) supported the findings. The sensing mechanism is rationalized in terms of radical cation formation upon ClO- oxidation of cyanine sensors I and II.

A test battery approach for ecotoxicological evaluation of disinfectants prepared on the basis of sodium hypochlorite

Abstract The research is related to the assessment of the overall sensitivity and applicability of many bioassays representing different trophic levels for the preliminary ecotoxicological testing of commercial disinfectants marked as SA (SAVO, Bochemie a.s., Czech Republic) and DoAm (Dom Amor, BOOS – Biologické substancie, Slovak Republic). Disinfectants were prepared based on sodium hypochlorite (NaOCl). SA contains only NaOCl while earthworm enzymes enrich DoAm. In both commercial products, the NaOCl content did not exceed 5%; pure NaOCl was used as a 10% solution as well. For bioassay, water organisms (Vibrio fischeri, Desmodesmus subspicatus, Daphnia magna and Tubifex tubifex) situated in various trophic levels were used. All the tests were confirmed as suitable for the determination of chlorine’s adverse effects. Because the organisms’ reactions to the tested disinfectants varied, they can be arranged in the following rank order of sensitivity: V. fischeri ≥ D. subspicatus &gt;&gt; D. magna &gt;&gt; T. tubifex. The toxicity of the tested substances (NaOCl, SA, DoAm) depends on the length of exposure, the species of the organism and FAC (free available chlorine) content. The effective concentrations of the tested products ranged from 0.13 to 8.18 μL L–1, i.e., 0.014 to 0.26 mg L–1 of FAC. However, in the tests with T. tubifex and V. fischeri the toxic effect of NaOCl was the weakest; the tests with other two organisms confirmed this compound as the most toxic. Only for T. tubifex (96 hrs) did SA have a more adverse effect than DoAm.

Corrigendum to Determination of fluorine and chlorine in standard steel residues and zinc sulfide concentrates by ion chromatography-matrix interference study: [Chinese Journal of Analytical Chemistry 51 (2023) 1–8/100147

Corrigendum to Determination of fluorine and chlorine in standard steel residues and zinc sulfide concentrates by ion chromatography-matrix interference study: [Chinese Journal of Analytical Chemistry 51 (2023) 1–8/100147

Direct determination of chlorine in the glycerin by-product of biodiesel production: A green approach using energy dispersive X-ray fluorescence spectrometry

Glycerin, by-product of biodiesel, is produced in large amounts and it contains several contaminants, including chorine (due to the neutralization stage using HCl). When using this glycerin as biomass to produce energy, the presence of alkaline chlorides may lead to the formation of corrosive fumes at high temperatures. In this sense, the knowledge of chloride content is important in order to decide the fate of this raw by-product. The direct spectrometric determination of chlorine is an analytical challenge. In this context, energy-dispersive X-ray fluorescence spectrometry provided direct and accurate determination, relying on external calibration based on sample dilution and matrix matching with mixture of pure glycerin and water and using NaCl as the analytical (primary) standard. Method limit of quantification was 50 mg kg−1, with analytical curve up to 1000 mg kg−1 (R2 = 0.9992), and repeatability below 5% were found to be adequate for such application in such highly salty samples (original concentrations at mg g−1). In addition to sample directly analysis, without any previous treatment but homogenization and dilution, not requiring chemical derivatization and the not using of toxic reagents are in consonance to the analytical green chemistry requirements, allowing direct analysis of sample with no chemical derivatization with toxic reagents.

Determination of fluorine and chlorine in standard steel residues and zinc sulfide concentrates by ion chromatography-matrix interference study

1 Ion chromatographic based determination of F − and Cl − . 2 Investigation of the effect of matrix constituent elements on F − and Cl − recovery. 3 Digestion of steel residues and zinc sulfide concentrate standard samples. 4 Various parameters of alkali fusion were optimized. The sensitive determination of trace fluorine and chlorine contents in complex inorganic matrices such as steal residues and zinc sulfide concentrates is challenging cause difficulty in their digestion and presence of various matrix interferences species. Therefore, in this study, the effect of various constituent elements of geological samples including Ni, As, Ag, Pb, Hg, Co, SiO 2 , Bi, Sb, Cr, Zn, Cd, Ag, CaO, MgO, Al, Fe, KBr, and KI on the alkali-fused steam distillation-based recoveries of fluoride and chloride were investigated for better understanding the application of this method in various geological samples. Hence, a simple, cost-effective and modified alkali fusion-steam distillation-ion chromatography (SD-IC) method was developed for the sensitive and selective determination of halogens in standard steel resides and zinc sulfide concentrate samples. For optimum extraction of analytes various digestion parameters including alkali fusion amount, fusion temperature, and fusion time along with distillation volume were sequentially optimized. The developed method shows good linearity in the range 0.2 - 3.0 mg/kg with correlation coefficient (r) values greater than 0. 99991. The limit of detection for fluoride and chloride were appeared 0.07326 mg/kg and 0.02331 mg/kg, respectively with precision (repeatability and the intermediate precision) less than 4.12%. The results of standard steal residue and zinc sulfide concentrate samples were in good agreement (91.27- 100.18%) with their certified reference values (CRMs). SD-IC is a simple, cost-effective, and sensitive method for the determination of fluoride and chloride contents in complex geological samples (steal residues and zinc sulfide concentrates).

Determination of chlorine in Hf precursors by high-resolution inductively coupled plasma mass spectrometry

This method can detect all remaining chlorine using HR-ICP-MS in a short time without complicated pretreatment conditions, minimizing pollutants.

Poly(caffeic acid) Redox Couple Decorated on Electrochemically Reduced Graphene Oxide for Electrocatalytic Sensing Free Chlorine in Drinking Water

Regular water quality measurements are essential to the public water supply. Moreover, selective free chlorine (disinfectant) level monitoring without an interfering agent is necessary. The present work aimed to fabricate poly(caffeic acid) (p-CFA) coated on an electrochemically reduced graphene oxide (ERGO) surface for the selective detection of free chlorine. Electron microscopy and various spectroscopic techniques confirmed the p-CFA@ERGO/glassy carbon (GC) electrode. The p-CFA@ERGO/GC coated probe surface coverage was calculated to be 4.75 × 10-11 mol cm-2. The p-CFA@ERGO/GC showed superior catechol/o-quinone oxidation/reduction peaks for electrocatalytic free chlorine determination. The performance of the developed sensor electrode was outstanding, with an extensive range of free chlorine detection (20 μM to 20 mM), high sensitivity (0.0361 µA µM-1), and low detection limit (0.03 µM). The p-CFA@ERGO/GC capability of the realist water samples, such as the tested commercial and tap water, yielded a good range of recovery (from 98.5% to 99.9%). These values align with the standard N,N'-diethyl-p-phenylenediamine reagent method results.

Separation and determination of boron, chlorine, fluorine and molybdenum in uranium silicide using pyrohydrolysis and ion chromatography

Separation and determination of boron, chlorine, fluorine and molybdenum in uranium silicide using pyrohydrolysis and ion chromatography

Boron-Doped Diamond as a Quasi-Reference Electrode.

As a working electrode, boron-doped diamond (BDD) has been studied in detail in electrochemical processes because of its superior electrochemical properties. However, these characteristics have rarely been mentioned when BDD is used as a quasi-reference electrode (QRE). Herein, we conducted a systematic investigation on BDD electrodes, with different boron-doping levels (1 and 0.1%) and different surface terminations (hydrogen and oxygen) for their application as a QRE. A BDD electrode with 1% boron and a hydrogen-terminated surface achieved the best stability. Its open-circuit potential (OCP) exhibited less than 100 mV of potential drift over 6000 s and showed a minuscule half-wave potential difference (E1/2) of 0.0037 V in 0.1 mM K3[Fe(CN)6]/1 M KCl solution before and after the OCP measurement. Based on these observations, anions are found to contribute to the potential, which we preliminarily speculate as related to the capacitance caused by electrostatic adsorption on the positively charged hydrogen-terminated surface. The repeatability of measurement was verified through continuous cyclic voltammetry tests in 0.1 mM K3[Fe(CN)6]/1 M KCl, showing a maximum E1/2 difference of 0.042 V. The contribution of the redox couples was excluded, and the repeatability was considered to originate from its surface stability. Finally, a linear response of the optimized BDD as a QRE was validated (R2 > 0.99) by determination of free chlorine and dopamine concentrations, respectively. These results consolidate the existing fundamental research on BDD electrodes and promote the possibility of its application as a QRE in harsh environments or in vivo biological monitoring.

Flow-based green ceramics microdevice with smartphone image colorimetric detection for free chlorine determination in drinking water

The residual free chlorine concentration is an important parameter to evaluate the potability of water and the efficiency of disinfection in the water treatment system. As a restricted range of residual free chlorine concentration at all points of the distribution network is needed to ensure efficiency and to avoid deleterious effects, fast and in situ quantification of this specie is important. This work deals with the development and validation of two procedures based on DPD (N,N-diethyl-p-phenylenediamine) and OT (ortho-tolidine, 3,3-dimethylbenzidine) for the determination of residual free chlorine in water by exploiting a flow-based microdevice built with Low Temperature Co-Fired Ceramic (LTCC) technology. The analytical signal was monitored by a smartphone camera through RGB values obtained by a free application (Color Grab®). Under optimized conditions, linear ranges within 0.6–2.5 mg/L and 0.1–2.3 mg/L were obtained for DPD and OT methods, with limits of detection and quantification of 0.023 and 0.077 mg/L (DPD) and 0.026 and 0.089 mg/L (OT). Precision expressed as RSD (2.0 mg/L free chlorine, n = 10), was 1.3 % and 0.7 %, respectively. Both procedures were successfully applied to the analysis of samples from a water treatment plant. The flow-based microdevice coupled to digital-image colorimetry is an innovative, sustainable, and cost-effective analytical tool for in-field chemical analysis.