Ion-exchange Chromatography Research Articles

A compact and high-performance setup of capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D).

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) has the advantages of high throughput (simultaneous detection of multiple ions), high separation efficiency (higher than 105 theoretical plates) and rapid analysis capability (less than 5 min for common inorganic ions). A compact CE-C4D system is ideal for water quality control and on-site analysis. It is suitable not only for common cations (e.g. Na+, K+, Li+, NH4+, Ca2+, etc.) and anions (e.g. Cl-, SO42-, BrO3-, etc.) but also for some ions (e.g. lanthanide ions, Pb2+, Cd2+, etc.) that require complex derivatization procedures to be detected by ion chromatography (IC). However, an obvious limitation of the CE-C4D method is that its sensitivity (e.g. 0.3-1 μM for common inorganic ions) is often insufficient for trace analysis (e.g. 1 ppb or 20 nM level for common inorganic ions) without preconcentration. For this technology to become a powerful and routine analytical technique, the system should be made compact while maintaining trace analysis sensitivity. In this study, we developed an all-in-one version of the CE-C4D instrument with custom-made modular components to make it a convenient, compact and high-performance system. The system was designed using direct digital synthesis (DDS) technology to generate programmable sinusoidal waveforms with any frequency for excitation, a kilovolt high-voltage power supply for capillary electrophoresis separation, and an "effective" differential C4D cell with a low-noise circuitry for high-sensitivity detection. We characterized the system with different concentrations of Cs+, and even a low concentration of 20 nM was detectable without preconcentration. Moreover, the optimized CE-C4D setup was applied to analyse mixed ions at a trace concentration of 200 nM with excellent signal-to-noise ratios. In typical applications, the limits of detection based on the 3σ criterion (without baseline filtering) were 9, 10, 24, 5, and 12 nM for K+, Cs+, Li+, Ca2+, and Mg2+, respectively, and about 7, 6, 6 and 6 nM for Br-, ClO4-, BrO3- and SO42-, respectively. Finally, the setup was also applied for the analysis of all 14 lanthanide ions and rare-earth minerals, and it showed an improvement in sensitivity by more than 25 times.

Identification and enzymatic properties of arginine decarboxylase from Aspergillus oryzae.

Aspergillus oryzae spores, when sprinkled onto steamed rice and allowed to propagate, are referred to as rice "koji." Agmatine, a natural polyamine derived from arginine through the action of arginine decarboxylase (ADC), is abundantly produced by solid state-cultivated rice koji of A. oryzae RIB40 under low pH conditions, despite the apparent absence of ADC orthologs in its genome. Mass spectrometry imaging revealed that agmatine was accumulated inside rice koji at low pH conditions, where arginine was distributed. ADC activity was predominantly observed in substrate mycelia and minimally in aerial mycelia. Natural ADC was isolated from solid state-cultivated A. oryzae rice koji containing substrate mycelia, using ammonium sulfate fractionation, ion exchange, and gel-filtration chromatography. The purified protein was subjected to sodium dodecyl sulfate poly-acrylamide gel electrophoresis (SDS-PAGE), and the detected peptide band was digested for identification by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The gene AO090102000327 of strain RIB40 was identified, previously annotated as phosphatidylserine decarboxylase (PSD), and encoded a 483-amino acid peptide. Recombinant protein encoded by AO090102000327 was expressed in Escherichia coli cells cultivated at 20°C, resulting in the detection of 49 kDa and 5 kDa peptides. The protein exhibited pyruvoyl-dependent decarboxylase activity, favoring arginine over ornithine and showing no activity with phosphatidylserine. The gene was designated Ao-adc1. Ao-ADC1 expression in rice koji at pH 4-6 was confirmed through western blotting using the anti-Ao-ADC1 serum. These findings indicate that Ao-adc1 encodes arginine decarboxylase involved in agmatine production.IMPORTANCEGene AO090102000327 in A. oryzae RIB40, previously annotated as a PSD, falls into a distinct clade when examining the phylogenetic distribution of PSDs. Contrary to the initial PSD annotation, our analysis indicates that the protein encoded by AO090102000327 is expressed in the substrate mycelia area of solid state-cultivated A. oryzae rice koji and functions as an arginine decarboxylase (ADC). The clade to which Ao-ADC1 belongs includes three other Ao-ADC1 paralogs (AO090103000445, AO090701000800, and AO090701000802) that presumably encode ADC rather than PSDs. Regarding PSD, AO090012000733 and AO090005001124 were speculated to be nonmitochondrial and mitochondrial PSDs in A. oryzae RIB40, respectively.

PURIFICATION AND CHARACTERIZATION OF AMYLASE PRODUCED FROM PROBIOTIC LACTOBACILLUS PLANTARUM CS FOR INDUSTRIAL APPLICATIONS

Previous studies have demonstrated that probiotic Lactobacillus plantarum CS was able to generate an appreciable amount of extracellular amylase, hence the need to purify and characterize it. The aim of the study was to purify and characterize crude amylase from probiotic Lactobacillus plantarum CS for its industrial applications Three purification steps including ammonium sulphate precipitation, ion exchange chromatography on carboxymethyl sephadex and gel filtration on Sephadex G-75 were utilized. The homogeneity of the purified enzyme was confirmed using sodium deodocyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE). The purified amylase was characterized on different parameters including substrates hydrolyses, pH and temperature activity and stability profiles. The general purification elution profile revealed two different peaks of amylase activities with outstanding one having a molecular weight of 59.7kDa. Its purification fold was 4.0 with specific activity of 16.44U/mg protein and enzyme yield of 3%.  Temperature optimal activity and stability was at 400C and 7.5 for pH activity and stability. Mangenese (Mn2+) (135.17%), tween 80 (128.30%) and some food condiments garlic, thyme, ginger, and tumeric) significantly (p> 0.05) enhanced amylase activity (≥262.40%). However, selenium (Se4+) and hydrogen peroxide (H2O2) were observed to have greatest inhibiting effect (≥30.9%) on the enzyme. Substrate hydrolysis profiles showed that the amylase hydrolyzed all the test starchy substrates with the highest hydrolytic potential on indigenous sweet potato starch (Km value/ Vmax of 1.33mg/ml/ 7.89ml). The rate of hydrolysis of other test substrates had yam> rice>cassava>corn with km values ≤ 4.0mg/ml and Vmax ≤ 25ml.  The obtained results gave an insight that amylase produced from Lactobacillus plantarum CS met with the possessed properties suitable for any industrial application especially in food

Oligonucleotide Purification by Ion Exchange Chromatography: A Step-by-Step Guide to Process Understanding, Modeling, and Simulation

Oligonucleotide Purification by Ion Exchange Chromatography: A Step-by-Step Guide to Process Understanding, Modeling, and Simulation

Alocasia macrorrhiza rhizome lectin inhibits growth of pathogenic bacteria and human lung cancer cell in vitro and Ehrlich ascites carcinoma cell in vivo in mice

Cancer and antibiotic resistance represent significant global challenges, affecting public health and healthcare systems worldwide. Lectin, a carbohydrate-binding protein, displays various biological properties, including antimicrobial and anticancer activities. This study focused on anticancer and antibacterial properties of Alocasia macrorrhiza lectin (AML). AML, with a molecular weight of 11.0 ± 1.0 kDa was purified using Ion-exchange chromatography, and the homotetrameric form was detected by gel-filtration chromatography. It agglutinates mouse erythrocytes, that was inhibited by 4-Nitrophenyl-α-D-mannopyranoside. Maximum hemagglutination activity was observed below 60°C and within a pH range from 8 to 11. Additionally, it exhibited moderate toxicity against brine shrimp nauplii with LD50 values of 321 μg/ml and showed antibacterial activity against Escherichia coli and Shigella dysenteriae. In vitro experiments demonstrated that AML suppressed the proliferation of mice Ehrlich ascites carcinoma (EAC) cells by 35% and human lung cancer (A549) cells by 40% at 512 μg/ml concentration. In vivo experiments involved intraperitoneal injection of AML in EAC-bearing mice for five consecutive days at doses of 2.5 and 5.0 mg/kg/day, and the results indicated that AML inhibited EAC cell growth by 37% and 54%, respectively. Finally, it can be concluded that AML can be used for further anticancer and antibacterial studies.

Comparison of continuous flow analysis and ion chromatography for determinations of nitrate, nitrite and phosphate ions in seawater and development of related seawater certified reference materials

Comparison of continuous flow analysis and ion chromatography for determinations of nitrate, nitrite and phosphate ions in seawater and development of related seawater certified reference materials

Adjustable chromatographic performance of silica-based mixed-mode stationary phase through the control of co-grafting amounts of imidazole and C18 chain

In this paper, three imidazole- and C18- bifunctional silica stationary phases (Sil-Im-C18) were prepared by adjusting introduction interval of octadecyltrichlorosilane (ODS) and 3-imidazol-1-ylpropyl(trimethoxy)silane (TMPImS), which can be used for reversed-phase liquid chromatography (RPLC) and ion exchange chromatography (IEC) with adjustable performance. The successful preparation of Sil-Im-C18 were confirmed by the characterizations of elemental analysis, infrared spectroscopy (FTIR) and contact angle (CA). Chromatographic performance of Sil-Im-C18 were evaluated by the separation of Tanaka test mixture, alkylbenzenes, linear PAHs and a set of analytes with different properties (uracil, phenol, 1,2-dinitrobenzene and naphthalene), and compared with commonly used C18 column. It was found that the chromatographic performance of Sil-Im-C18 changed significantly with the difference in bonding amount of imidazole and C18. Sil-Im-C18 demonstrated the excellent separation performance towards polycyclic aromatic hydrocarbons (PAHs), phenylesters, phenylamines, phenols and inorganic anions, and notably, nucleobases and nucleosides can be separated using pure water as mobile phases. The van Deemter plot showed that the column efficiency of Sil-Im-C18-3 was 64,933 plate·m−1 for naphthalene, indicated that Sil-Im-C18 was reasonably chromatographic columns. The RSD values of retention time were 0.22 %-0.61 % for 10 needles alkylbenzenes injected continuously at 50 °C to investigate thermal stability and repeatability, all the fluctuations of k of naphthalene were less than 2.3 % for Sil-Im-C18-1 during flushing 24 h with the mobile phase at different pH values (pH = 3 and 8), the retention time of alkylbenzenes were almost same for Sil-Im-C18-1 at different time, the RSD values of retention time of alkylbenzenes were 0.45 %-2.28 % for two batches Sil-Im-C18-1, revealing the excellent repeatability, thermal stability, durability and reproducibility of Sil-Im-C18, and implying a commercial prospect.

Comparison of three methods for collecting interstitial fluid from subcutaneous tissue in mini pigs

Interstitial fluid, owing to its similarity to blood components and higher sensitivity and specificity, finds widespread application in disease diagnosis and tumor marker detection. However, collecting interstitial fluid, particularly from the deep subcutaneous connective tissue, remains challenging.•This study aimed to compare three different collection methods - push-pull perfusion, multi-filament nylon thread implantation, and tissue centrifugation - for collecting interstitial fluid from the subcutaneous connective tissue layer of mini-pigs. High-performance ion chromatography was employed to analyze the conventional cation components in the samples and compare ion composition analysis between the different methods.•Results indicated that while the distribution of conventional cations in the interstitial fluid collected by the three methods was generally consistent, there were slight variations in the detection rates and concentrations of different ions. Hence, suitable collection methods should be selected based on the ions or collection sites of interest.

Study on the transient expression of infectious bronchitis virus spike protein in Nicotiana benthamiana leaves

Infectious bronchitis virus (IBV) is considered as one of the main causes of economic loss in chicken farms worldwide, especially in poultry producing nations. This virus, a member of the Coronaviridae family, is classified into different genotypes based on its surface spike glycoproteins which also play important roles in cell attachment and immune response. Due to continual genetic mutation of IBV, attenuated and inactivated vaccines show decreased effectiveness or lack of cross – protection; thus ongoing studies focus on the development of new generation vaccines to prevent new IBV outbreaks. This paper describes our study on expression of the antigenic region in S1 subunit of the spike in Nicotiana benthamiana. Two expression vectors carrying either S1 or receptor binding domain (RBD) coding gene (pCB301-S1 and pCB301-RBD) were constructed and transformed into tobacco leaves by agroinfiltration method. The RBD showed a clearly higher level of expression compared to the whole S1. Purification of RBD by immobilized metal ion chromatography and size exclusion chromatography represented a mixture of monomer, dimer and trimer glycoprotein with expected sizes in Western blot. In summary, this study demonstrated our primary success in establishing an expression model that could be used to investigate plant-based IBV recombinant vaccine.

Influences of alumina type and sulfate content on hydration and physicochemical changes in Portland–limestone cement

This study explored the influence of alumina type and gypsum content on the hydration, mechanical properties, and chemical changes of Portland–limestone cement (PLC) using isothermal calorimetry, inductively coupled plasma-optical emission spectroscopy (ICP-OES), ionic chromatography (IC), compressive strength testing, X-ray diffraction (XRD), 27Al magic angle spinning nuclear magnetic resonance (27Al MAS NMR) spectroscopy, and mercury intrusion porosimetry (MIP) testing. The addition of alumina shortened the induction period, accelerated the acceleration period, and increased the mechanical strength of the PLC pastes with 3 and 7 wt% gypsum. The acceleration effect and strength enhancement were not distinct in the PLC pastes with less gypsum (0.1 wt%). The addition of γ-alumina led to the greatest accelerating effect and strength improvement in the PLC pastes with 3 and 7 wt% gypsum, and the compressive strength achieved was comparable to those of pure Ordinary Portland cement (OPC) pastes without limestone. The addition of γ-alumina induced the rapid dissolution of gypsum and consumption of sulfate ions. The chemical change affected by the addition of alumina varied greatly depending on the gypsum content, and trends in AFt and AFm formation in the PLC pastes with different gypsum contents were confirmed. Finally, pore size refinement was observed through the addition of alumina to PLC pastes with 3 and 7 wt% gypsum.

Purification, and characterization of a new pro-coagulant protein from Iranian Echis carinatus venom

This work aimed to purify the proteins that cause blood coagulation in the venom of the Iranian Echis carinatus snake species in a comprehensive manner. Gel filtration chromatography (GFC), Ion exchange chromatography (IEC), and Size Exclusion High-Performance Liquid Chromatography (SEC-HPLC) were utilized in the purification of the coagulation factors. The prothrombin clotting time (PRCT) and SDS-PAGE electrophoresis were performed to confirm the coagulative fractions. The fraction with the shortest coagulation time was selected. The components of this designated fraction were identified through matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF) following thorough purification. Circular dichroism (CD) was employed to determine the second structure of the coagulation factor. The crude venom (CV) was analyzed and had a total protein concentration of 97%.Furthermore, the PRCT of the crude venom solution at a concentration of 1 mg/ml was determined to be 24.19 ± 1.05 s. The dosage administered was found to be a factor in the venom's capacity to induce hemolysis. According to CD analysis, the protein under investigation had a helical structure of 16.7%, a beta structure of 41%, and a turn structure of 9.8%. CHNS proved that the purified coagulant protein had a Carbon content of 77.82%, 5.66% Hydrogen, 3.19% Nitrogen, and 0.49% Sulphur. In the present investigation, a particular type of snake venom metalloproteinase (SVMP) has undergone the process of purification and characterization and has been designated as EC-124. This purified fraction shows significant efficacy as a procoagulant. Our findings have shown that this compound has a function similar to factor X and most likely it can cause blood coagulation by activating factor II (FII).

Determination of phosphorus in commercially available milk using ion chromatography with perchloric acid deproteinization.

Suppressed ion chromatography with perchloric acid deproteinization was developed for the determination of phosphorus in commercially available milk. Although the perchloric acid deproteinization method is widely used in the medical field, it sees limited application in the food industry. Herein, the concentration of perchloric acid and hydrolysis conditions were examined, specifically regarding perchloric acid deproteinization, which was used as a deproteinization method in this study. The calibration curve constructed from the peak area of orthophosphoric acid (monohydrogen phosphate ion: HPO42-) was linear, with a correlation coefficient of 0.999. The relative standard deviation of the peak area of 50mg/L of HPO42- from six replicates was 0.35%. The detection and quantitative limits of HPO42-, calculated from its signal-to-noise ratio were 0.033mg/L and 0.100mg/L, respectively. The proposed method was applied to the analysis of phosphorus in commercially available milk. Perchloric acid deproteinization has proved to be useful in the food industry.

Design and optimization of a continuous purification process using ion-exchange periodic counter-current chromatography for a low-titer enzyme

AbstractA continuous purification process can be beneficial to the purification of biologics due to its higher productivity and efficiency than a conventional batch purification process. However, regulatory issues and lack of established cases render deployment of the continuous process difficult in industrial settings. Here we report a case study for design and optimization of an advanced continuous process for purifying a low-titer enzyme as a model biologic. To convert a conventional batch process to an advanced continuous one in purification of biologics, conventional unit operations (UOs), including ultrafiltration/diafiltration (UF/DF) and batch chromatography, were replaced by advanced ones such as in-line dilution conditioning (IDC) and periodic counter-current chromatography (PCC). The UF/DF UO was changed to IDC UO to adjust pH and conductivity. The mixing ratio of the sample and the conditioning buffer in IDC was determined by experiments with three buffers. PCC was optimized with two variables, column height and sample loading residence time, as the delta pressure in the columns was less than 1.0 bar. A graph indicating the operating area was plotted to efficiently control the PCC. Although the sample volume increased in IDC, PCC had a complementary advantage in that purification was performed faster than batch chromatography. We observed at least 25% increase in economic advantage when the advanced continuous process was applied to purify a low-titer enzyme. We propose not only a continuous process with the substitution of UF/DF and batch chromatography with IDC and PCC but also a method to optimize PCC by plotting operating areas.

Determination of benzoate in cranberry and lingonberry by using a solid-contact benzoate-selective electrode

Benzoic acid is used as a preservative in processed food, and occasionally in cosmetics and pharmaceuticals, while benzoic acid occurs naturally in, e.g., cranberry and lingonberry. Therefore, the determination of benzoate is of interest for product quality assurance, food safety, and personal health. In this work, a solid-contact benzoate-selective electrode (benzoate-ISE) was developed by utilising poly(3,4-ethylenedioxythiophene) (PEDOT) as solid contact and a solvent polymeric membrane containing a 1,3-bis(carbazolyl)urea derivative as ionophore. The benzoate-ISE was characterised in parallel with an ionophore-free control-ISE by electrochemical impedance spectroscopy and potentiometry. The presence of the ionophore in the membrane improved the selectivity to benzoate. Benzoate-ISEs and control-ISEs were used further to determine the benzoate concentration in cranberry and lingonberry by standard addition. The results obtained with both types of ISEs were compared with those obtained by ion chromatography. The results obtained with benzoate-ISEs were consistent with those obtained with ion chromatography. On the contrary, the control-ISE (without ionophore) gave significantly higher benzoate concentrations, especially in the case of cranberry where the benzoate concentration was low (ca 0.2 g kg−1) compared to lingonberry (ca 1 g kg−1). Hence, the benzoate-selectivity of the ionophore was crucial to obtain a benzoate-ISE that was practically applicable for determination of benzoate concentrations in cranberry and lingonberry.

Superhydrophobic eggshell for fabrication of hydrophobic barrier of paper-based analytical device for colorimetric determination of ammonium ion in water

This work demonstrates the first application of the superhydrophobic eggshell as an environmental-friendly material for fabricating the hydrophobic barrier of a paper-based analytical device (PAD). The eggshell surface was modified by mixing the pulverized chicken eggshell biowaste with stearic acid and a polystyrene binder to accomplish superhydrophobicity. The PAD (10 × 10 mm2) is comprised of the circular-shaped hydrophilic reservoir (Ø 5 mm). The liquid barrier was fabricated by painting both the topside and the underside of the filter paper with the dispersed superhydrophobic eggshell solution. The SEM images revealed that the microsized superhydrophobic eggshell particles absorbed onto the porous surface of the cellulose fibril. A coated surface with a water contact angle of 155.39° ± 1.02° (n = 10) on the paper substrate was achieved, and this indicated superhydrophobicity. The eggshell barrier enabled excellent water and chemical resistance. The fabricated PAD was applied for the colorimetric determination of ammonium cations (NH4+), based on the modified Berthelot reaction. Samples and chromogenic solutions were aliquoted onto the hydrophilic reservoir, with subsequent capture of the optical image of the stable, green-colored product by a smart phone under a light-controlled studio. The green color intensities were evaluated by ImageJ™ and plotted against the standard NH4+ concentrations. A wide linear calibration range 5.0 to 100 mg N/L was achieved with good linearity (r2 > 0.99). The PAD confirmed satisfied analytical recovery (Mean ± SD: 100.6 % ± 0.97, n = 11 samples) and high precision (RSD = 0.85 %: 10-PAD replicate measurements of 1.0 mg N/L). The limit of detection (3 SD of blank/slope) of 1.05 mg N/L was found sensitive enough to monitor the NH4+ contents in freshwater. The results, determined by the developed PAD and ion chromatography, showed no significant difference under the statistical paired t-test at 95 % confidence (tstat = -1.80, tcri = 2.57, n = 6 samples).

Application of a portable ion chromatograph for real-time field analysis of nitrite and nitrate in soils and soil pore waters

Real-time monitoring of nitrite and nitrate is crucial for maintaining soil health and promoting plant growth. In this study, a portable ion-chromatograph (IC, Aquamonitrix) analyser, coupled with a field-applicable ultrasonic-assisted extraction method, was utilised for in-field determination of nitrate and nitrite in soils. This is the first application of this type of analyser to soil nutrients. On-site analysis of soil from a local sports field showed 94.8 ± 4.3 μg g−1 nitrate, with LODs of 32.0 μg g−1 for nitrate and 5.4 μg g−1 for nitrite. The results were in close agreement with those obtained using a conventional lab-based IC. Relative standard deviations (%RSDs) for soil analysis using Aquamonitrix were consistently below 10%. The obtained average recoveries of samples spiked with nitrite were 100% and 104% for the portable IC and conventional IC, respectively. Furthermore, to assess the suitability of portable IC for samples with high organic matter content, various natural organic fertilisers were extracted and analysed. The results showed 16.2 ± 0.7 μg g−1 nitrite and 28.5 ± 5.6 μg g−1 nitrate in sheep manure samples with LODs of 2.0 μg g−1 for nitrite and 12.0 μg g−1 for nitrate. The portable IC system was further demonstrated via real-time on-site analysis of soil pore-water acquired using a portable battery-based ceramic pore-water sampler. A continuous increase in nitrate concentration over time was observed (from 80 to 148 μg mL−1) in the soil pore-water in a vegetable garden four days after heavy rain. Unlike conventionally sampled natural waters, 7-day storage of the studied pore water samples revealed no changes in nitrate concentrations. An average of 558 ± 51 μg mL−1 nitrate was detected in the soil pore-water samples analysed on a spinach farm, immediately after irrigation.

Split-ring resonator with interdigital Split electrodes as detector for liquid and ion chromatography

The analysis of food and drugs as well as the monitoring of chemical processes and bioreactors by high-performance liquid chromatography and ion chromatography requires universal, cost-effective, and sensitive detectors. Therefore, this work presents a split-ring resonator that detects changes in the electrical and dielectric properties of the eluate from liquid chromatography or ion chromatography by monitoring the amplitude of the transmitted signal using an envelope detector. The used split-ring resonator consists of a simple printed circuit board featuring two microstrip lines. One is formed to a ring with interdigital split electrodes. The interdigital split electrodes forming the sensitive area significantly enhance the sensitivity to changes in relative permittivity, dielectric losses and electrical conductivity of the eluate In addition, the split-ring resonator is a small, inexpensive and easy-to-use detector that uses several dielectric parameters simultaneously for the measurement. Furthermore, the split-ring resonator measures these parameters at a significantly lower frequency than optical detectors and therefore measures different changes in frequency-dependent permittivity. For demonstrating feasibility of a split-ring resonator as a detector for high-performance liquid chromatography and ion chromatography, various anion and cation standards, basic and acidic amino acids, sugars, as well as sugar alcohols were separated and detected. A conductivity detector for ion chromatography and a refractive index detector for high-performance liquid chromatography were used as reference detectors.

Quantification of Major Inorganic Contaminants in a Mediterranean Coastal Lagoon with a Large Dystrophic Crisis.

In August 2021, the Mar Menor, a saltwater lagoon located in the Region of Murcia (Spain), suffered a tragic environmental episode of dystrophic crisis and anoxia. The appearance of numerous dead fish in different areas of the lagoon over the course of days put all the authorities and the population of the area on alert. This paper shows a case study of what happened in the lagoon in terms of the presence of the most common inorganic pollutants. Measurements of the concentration of nitrogen species, phosphates and main heavy metals were carried out at different sampling sites in the Mar Menor from May 2021 to November 2022. Chemical analyses were carried out for each of the species under study. These analyses provide valuable information about the dystrophic crisis caused by a classic eutrophication process that began with the excessive nutrient input into the Mar Menor. Ion chromatography and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) were used as instrumentation for the quantification of these samples. The species whose values were greatly increased after the tragic episode described above were nitrates. The concentration varied significantly at the different sampling sites throughout the study. On the last sampling date, decreased concentrations of all the species were measured at each of the sampling sites, coinciding with the apparent good state of the lagoon.

Fabrication and application of a continuously regenerated cationic impurity removal device for ion chromatography

A continuously regenerated cationic impurity removal device (CR-CRD) has been fabricated and applied for ion chromatography (IC). The removal of cationic impurities is realized by electrodialytically replacing the cationic impurities with hydronium ions. The device is configured in a sandwich structure and the central eluent channel is respectively isolated from both electrodes by stacked cation exchange membranes and a bipolar membrane (BPM) plus stacked anion exchange membranes. The eluent channel is packed with cation exchange resins in hydronium form and their continuous regeneration can be achieved by electrodialysis. A desirable feature of the device is gas-free, and no degasser is required. It showed sufficient ability to remove cationic impurities, as indicated by >99.9% removal of 10 mL of 1 mM LiOH solution injected (∼10 μmol) or continuous removal of 1 mM LiOH solution at the flow rate of 1 mL/min (1 μmol/min). A useful application was for sample pretreatment in nuclear power industry, by eliminating strong matrix interference of the sample containing LiOH (1 mM) and boric acid (2000 mg/L) with trace anion analysis.

Urinary biomonitoring of glyphosate exposure among male farmers and nonfarmers in the Biomarkers of Exposure and Effect in Agriculture (BEEA) study

Glyphosate is the most widely applied herbicide worldwide. Glyphosate biomonitoring data are limited for agricultural settings. We measured urinary glyphosate concentrations and assessed exposure determinants in the Biomarkers of Exposure and Effect in Agriculture (BEEA) study. We selected four groups of BEEA participants based on self-reported pesticide exposure: recently exposed farmers with occupational glyphosate use in the last 7 days (n = 98), farmers with high lifetime glyphosate use (>80th percentile) but no use in the last 7 days (n = 70), farming controls with minimal lifetime use (n = 100), and nonfarming controls with no occupational pesticide exposures and no recent home/garden glyphosate use (n = 100). Glyphosate was quantified in first-morning-void urine using ion chromatography isotope-dilution tandem mass spectrometry. We estimated associations between urinary glyphosate concentrations and potential determinants using multivariable linear regression. Glyphosate was detected (≥0.2 µg/L) in urine of most farmers with recent (91 %) and high lifetime (93 %) use, as well as farming (88 %) and nonfarming (81 %) controls; geometric mean concentrations were 0.89, 0.59, 0.46, and 0.39 µg/L (0.79, 0.51, 0.42, and 0.37 µg/g creatinine), respectively. Compared with both control groups, urinary glyphosate concentrations were significantly elevated among recently exposed farmers (P < 0.0001), particularly those who used glyphosate in the previous day [vs. nonfarming controls; geometric mean ratio (GMR) = 5.46; 95 % confidence interval (CI) = 3.75,7.93]. Concentrations among high lifetime exposed farmers were also elevated (P < 0.01 vs. nonfarming controls). Among recently exposed farmers, glyphosate concentrations were higher among those not wearing gloves when applying glyphosate (GMR = 1.91; 95 %CI = 1.17,3.11), not wearing long-sleeved shirts when mixing/loading glyphosate (GMR = 2.00; 95 %CI = 1.04,3.86), applying glyphosate exclusively using broadcast/boom sprayers (vs. hand sprayer only; GMR = 1.70; 95 %CI = 1.00,2.92), and applying glyphosate to crops (vs. non-crop; GMR = 1.72; 95 %CI = 1.04,2.84). Both farmers and nonfarmers are exposed to glyphosate, with recency of occupational glyphosate use being the strongest determinant of urinary glyphosate concentrations. Continued biomonitoring of glyphosate in various settings is warranted.