[Determination of furosine in liquid milk by high performance liquid chromatography-quadrupole time-of-flight mass spectrometry].

Furosine is often used both domestically and internationally as an indicator of the degree of heating to evaluate milk quality. However, in actual detection, the complexity of the milk matrix may lead to the inaccurate quantification of furosine in liquid milk. Therefore, in this study, an efficient and accurate method based on high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC-Q-TOF/MS) was established to determine furosine in liquid milk. A 2.00 mL milk sample was hydrolyzed with 5 mL 12.00 mol/L hydrochloric acid solution and 1 mL water at 110 ℃ for 12 h. After hydrolysis, vortex-mixing and filtration were performed. The filtrate was diluted six times with 6.00 g/L ammonium acetate solution and then analyzed. Gradient elution was performed with 0.20% formic acid aqueous solution and acetonitrile solution as mobile phases, followed by chromatographic separation on an AQ-C18 column (150 mm×3.5 mm, 5 µm). The data were collected by Q-TOF/MS with an electrospray ionization source operated in positive-ion mode. The accuracy of the quantification of furosine in milk was assessed by investigating the effects of the hydrochloric acid concentration (0.30, 1.25, and 3.00 mol/L) in the furosine solution on the MS response. The results showed that high hydrochloric acid concentrations inhibited the response signals. A good linear relationship was obtained in the mass concentration range of 0.05-2.00 mg/L, with a correlation coefficient (r) of 0.994. The limit of detection of the method was 0.50 mg/100 g, which meets the requirements of actual sample detection. The average recoveries of furosine ranged from 79.9% to 119.7% at three spiked levels of 1.52, 3.03, and 15.17 mg/100 g, with relative standard deviations of 1.4%-2.6%. The method was applied to detect 303 samples from 101 batches of pasteurized milk sold in the market, and the contents of furosine in these samples ranged from 5.1 to 11.9 mg/100 g. The proposed method is characterized with high efficiency, recovery, sensitivity, and accuracy. Thus, it can be used for the determination of large quantities of samples and provides technical support for the continuous promotion of the high-quality development of the whole dairy industry chain.

Phosphoryl Trichloride-Method of Determination in Workplace Air.

The aim of this study was to develop and validate a method for determining phosphoryl trichloride in workplace air. The method is based on passing the tested air through a sodium carbonate-impregnated quartz fiber sampling filter. The substance collected on the sampling filter is extracted with ultrapure water. Phosphoryl trichloride is determined as chloride ions (the product of the hydrolysis of phosphoryl trichloride) in the obtained aqueous solutions by ion chromatography with conductometric detection. The developed method enables the determination of phosphoryl trichloride in the air in the concentration range from 0.004 to 0.160 mg/m3. The method is not applicable in the presence of phosphorus trichloride, hydrochloric acid, and its salts in the air. Good validation results were obtained. All requirements of the norm PN-EN 482 were met while developing and validating the method. This method can be used to measure workplace air in order to assess workers' occupational exposure.

[The use of ion chromatography for the determination of volatile inorganic acids in workplace air]. / Zastosowanie chromatografii jonowej do oznaczania lotnych kwasów nieorganicznych w powietrzu na stanowiskach pracy.

BACKGROUND: The presence of inorganic acids in the air poses a threat to the health of workers. Volatile inorganic acids, e.g., hydrochloric acid, hydrobromic acid and nitric acid, may cause respiratory, eye and skin irritation. The presented method uses ion chromatography to determine the concentrations of hydrochloric, hydrobromic and nitric acids in air samples. MATERIAL AND METHODS: The method is based on the collection of airborne volatile acids on impregnated quartz fiber filter, extraction of acids with deionized water, and analysis by ion chromatography with conductivity suppression. The separation was performed on the Dionex IonPac™ AS22 (4 × 250 mm) column for trace anion analysis. The carbonate/bicarbonate eluent was maintained at an isocratic flow rate of 1.2 ml/min. The calibration standard solutions have been covering the range of 0.2-5 mg/l of chloride, bromide and nitrate. RESULTS: The specified chromatographic conditions enable selective measurement of chloride, bromide and nitrate anions. The obtained mass concentration of each anion, having factored in the sample dilution, the conversion factor (to convert anion concentration to acid) and the volume of the air sample, allows the calculation of acid concentrations in the analyzed air. CONCLUSIONS: This method makes it possible to determine the concentration of hydrochloric acid, hydrobromic acid and nitric acid in the workplace air within the concentration range corresponding to 0.1-2 times the exposure limit value in Poland. The method meets the criteria for the performance of procedures for the measurement of chemical agents, listed in PN-EN 482. This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering. Med Pr. 2022;73(4):337-47.

Bifunctional Metal Meshes Acting as a Semipermeable Membrane and Electrode for Sensitive Electrochemical Determination of Volatile Compounds.

The monitoring of toxic inorganic gases and volatile organic compounds has brought the development of field-deployable, sensitive, and scalable sensors into focus. Here, we attempted to meet these requirements by using concurrently microhole-structured meshes as (i) a membrane for the gas diffusion extraction of an analyte from a donor sample and (ii) an electrode for the sensitive electrochemical determination of this target with the receptor electrolyte at rest. We used two types of meshes with complementary benefits, i.e., Ni mesh fabricated by robust, scalable, and well-established methods for manufacturing specific designs and stainless steel wire mesh (SSWM), which is commercially available at a low cost. The diffusion of gas (from a donor) was conducted in headspace mode, thus minimizing issues related to mesh fouling. When compared with the conventional polytetrafluoroethylene (PTFE) membrane, both the meshes (40 µm hole diameter) led to a higher amount of vapor collected into the electrolyte for subsequent detection. This inedited fashion produced a kind of reverse diffusion of the analyte dissolved into the electrolyte (receptor), i.e., from the electrode to bulk, which further enabled highly sensitive analyses. Using Ni mesh coated with Ni(OH)2 nanoparticles, the limit of detection reached for ethanol was 24-fold lower than the data attained by a platform with a PTFE membrane and placement of the electrode into electrolyte bulk. This system was applied in the determination of ethanol in complex samples related to the production of ethanol biofuel. It is noteworthy that a simple equation fitted by machine learning was able to provide accurate assays (accuracies from 97 to 102%) by overcoming matrix effect-related interferences on detection performance. Furthermore, preliminary measurements demonstrated the successful coating of the meshes with gold films as an alternative raw electrode material and the monitoring of HCl utilizing Au-coated SSWMs. These strategies extend the applicability of the platform that may help to develop valuable volatile sensing solutions.

Emissions Control of Hydrochloric and Fluorhydric Acid in cement Factories from Romania.

From the available statistical data, cement factories co-process a range of over 100 types of waste (sorted both industrial and household) being authorized for their use as combustion components in clinker ovens. Therefore, the level of emissions is different depending on the type of fuels and waste used. The amount of industrial and municipal co-processed waste in the Romanian cement industry from 2004 to 2013 was about 1,500,000 tons, the equivalent of municipal waste generated in a year for 18 cities with over 250,000 inhabitants. The objective of this paper was to evaluate the emission level of hydrochloric acid (HCl) and hydrofluoric acid (HF) at the clinker kilns at two cement factories in Romania for different annual time intervals and to do a comparative analysis, to estimate their compliance with legislation in force. The measurements results showed average emission levels of about 0.578 mg/Nm3 for HCl and about 0.100 mg/Nm3 for HF, in the first hours of the evening, but decreased at the beginning of the third tour, at about 0.385 mg/Nm3 for HCl, respectively, to about 0.085 mg/Nm3 for HF. The evolution of HCl and HF emission levels during the last 4 years showed a variable distribution of these acids.

Carbazole and fluorene polyaniline derivatives: Synthesis, properties and application as multiple stimuli-responsive fluorescent chemosensor.

Development of conjugated polymers with fluorescence sensing characteristics has received close attention from researchers in fields of environmental protection, biosensing and toxins detection on food. In this paper, novel polyaniline derivatives of poly(9-methyl-9H-carbazol-3-amine) and poly(9,9-dihexyl-9H-fluoren-2-amine) are prepared by facile chemical polymerization. Then they are characterized with NMR (Nuclear Magnetic Resonance), GPC (Gel Permeation Chromatography), XRD (X-Ray Diffraction), FT-IR (Fourier Transform Infrared spectroscopy), FL (Fluorescence spectrometry) and UV-vis (Ultraviolet-visible spectroscopy) characterizations and further applied to the fluorescence detection of different acids and amines. Moreover, the obtained poly(9-methyl-9H-carbazol-3-amine) displays excellent fluorescence properties in the detection for both acids and amines. Besides, this poly(9-methyl-9H-carbazol-3-amine) can not only be used for fluorescence detection in solution, but also can be prepared into solid state and applied in the gas phase fluorescence detection. This work has greatly expanded the scope of application to these polyaniline derivatives materials, opening a new path for the researches on multi-functional chemosensor.

Background element content in the lichen Pseudevernia furfuracea: a comparative analysis of digestion methods.

In bioaccumulation studies, the interpretation of pollutant contents in the target biomonitor has to be performed by assessing a deviation from an unaltered reference condition. A common strategy consists in the comparison with background element content (BEC) values, often built up by uncritically merging methodologically heterogeneous data. In this respect, the acid digestion of samples was identified as a major step affecting BEC data. Here, the analytical outcomes of two acid mixtures were compared on a set of matched paired samples of the lichen Pseudevernia furfuracea, a widely used biomonitor for which BEC values based on partial digestion were previously provided. The standard reference material BCR 482 (P. furfuracea) was used to validate analytical procedures consisting of either a HF total mineralization or an aqua regia partial one, both associated to ICP-MS multi-element analysis. In particular, the performance of the procedures was evaluated by comparing analytical results of field samples with the accuracy obtained on BCR aliquots (measured-to-expected percentage ratio). The total digestion showed a better performance for Al, As, Ba, Ca, Cd, Cu, Fe, Mn, Ni, Se, Sn, and Zn, whereas the opposite was found for Cr, Co, P, and S. Moreover, new BEC values were provided for P. furfuracea using a consolidated statistical approach, after a total sample digestion with hydrofluoric acid. The multivariate investigation of the background variability of 43 elements in 57 remote Italian sites led to the identification of geographically homogeneous areas for which BEC values are provided for use as reference in biomonitoring applications.

Modeling and optimization of process variables for HCl gas removal by response surface methodology.

In the present article, optimization of process variables has been done to maximize the removal efficiency of toxic HCl gas in a submerged self-priming venturi scrubber. Response surface methodology with central composite design has been chosen to predict the effect of process variables on the removal efficiency. A quadratic equation was found from this study to predict the removal efficiency and from the ANOVA test, the significance of process variables was evaluated. Regression analysis confirmed the suitability of the developed model by the higher R2 square value (0.9717). Optimum conditions were obtained as 55.18 m s-1 of throat gas velocity, 405.10 ppm of inlet HCl concentration and 0.0038 N of NaOH concentration in scrubbing liquid to achieve 90.80% of the HCl removal efficiency.

Estimating source strengths of HCl and SO2 emissions in the flue gas from waste incineration.

HCl and SO2 emission is one of the major concerns related to municipal solid waste incinerator (MSWI). In this study, a material flow analysis model was developed to estimate the HCl and SO2 concentrations in the MSWI flue gases (FGs), and their concentrations in the full-scale MSWI were monitored. The calculated concentrations of HCl and SO2 in the FG were 770-1300 mg/Nm3 and 150-640 mg/Nm3, respectively, in close agreement with the monitored values. More than 99% of Cl and 92% of S from the FG were captured into solid residues by the air pollution control (APC) systems. Moreover, since only 48.4%-67.5% of Cl and 21.3%-53.4% of S were transferred to the FG from the municipal solid waste (MSW), it was more reliable to estimate the source strengths and release amounts of HCl and SO2 in the FG based on the amounts of Cl and S in the APC residues (AR) and exhaust gas rather than in the MSW. This simple method is easily applicable and the estimated results could provide scientific basis for the appropriate design and operation of the APC systems as well as corrosion control of heat recovery systems.

Formation and emission of hydrogen chloride in indoor air.

To improve our understanding of chlorine chemistry indoors, reactive chlorine species such as hydrogen chloride (HCl) must be analyzed using fast time-response measurement techniques. Although well studied outdoors, sources of HCl indoors are unknown. In this study, mixing ratios of gaseous HCl were measured at 0.5 Hz in the indoor environment using a cavity ring-down spectroscopy (CRDS) instrument. The CRDS measurement rate provides a major advance in observational capability compared to other established techniques. Measurements of HCl were performed during three types of household activities: (a) floor exposure to bleach, (b) chlorinated and nonchlorinated detergent use in household dishwashers, and (c) cooking events. Surface application of bleach resulted in a reproducible increase of 0.1 ppbv in the affected room. Emissions of HCl from automated dishwashers were observed only when chlorinated detergents were used, with additional HCl emitted during the drying cycle. Increased mixing ratios of HCl were also observed during meal preparation on an electric element stovetop. These observations of HCl derived from household activities indicate either direct emission or secondary production of HCl via chlorine atoms is possible. Calculations of photolysis rate constants of chlorine atom precursors provide evidence that photolysis may contribute to indoor HCl levels.

Printed Colorimetric Arrays for the Identification and Quantification of Acids and Bases.

Solid supported colorimetric sensing arrays have the advantage of portability and ease of use when deployed in the field, such as crime scenes, disaster zones, or in war zones, but many sensor arrays require complex fabrication methods. Here, we report a practical method for the fabrication of 4 × 4 colorimetric sensor arrays, which are printed on nylon membranes, using a commercially available inkjet printer. In order to test the efficacy of the printed arrays, they were exposed to 43 analytes at concentrations ranging from 0.001 to 3.0 M for a total of 559 samples of inorganic and organic acids or bases including hydrochloric, acetic, phthalic, malonic, picric, and trifluoroacetic acid, ammonium hydroxide, sodium hydroxide, lysine, and water as the control. Colorimetric data from the imaged arrays was analyzed with linear discriminant analysis and k-nearest neighbors to determine the analyte and concentration with ∼88-90% accuracy. Overall, the arrays have impressive analytical power to identify a variety of analytes at different concentrations while being simple to fabricate.

Benzofurazan-based fluorophore for the selective determination of flupentixol dihydrochloride: Application to content uniformity testing.

One of the most commonly used drugs in treatment of schizophrenia is flupentixol dihydrochloride, therefore it is important to develop a simple, low cost and sensitive spectrofluorimetric method for the estimation of flupentixol dihydrochloride. The yellow fluorescent product that is generated from the nucleophilic substitution reaction of the free lone pair of the alcoholic hydroxyl group of the drug and 4-chloro-7-nitrobenzofurazan (NBD-Cl) in Mcllvaine buffer pH 7.0 was estimated at 510 nm (λex 460 nm). The variables that affect the development of the reaction product were explored and optimized. The linear range of this method was 0.5-2.5 µg ml-1 with a limit of quantitation equal to 0.29 µg ml-1 . Our method was successfully applied for the assurance of flupentixol in tablet form with average percentage recovery of 99.08 ± 1.01% without obstruction from the basic excipients exhibits. Furthermore, our strategy was extended to study the content uniformity testing of flupentixol in Fluaxnol® tablets.

Repeated attempted homicide by administration of drugs documented by hair analysis.

Attempted murder by repeated poisoning is quite rare. The authors describe the case of a 62-year-old man who was admitted to an intensive care unit (ICU) for neurological disturbances complicated by inhalation pneumopathy. He presented a loss of consciousness while his wife was visiting him at the ICU (H0). Forty-eight hours later (H48), police officers apprehended the patient's wife pouring a liquid into his fruit salad at the hospital. Toxicological analyses of a blood sample and the infusion equipment (H0), as well as the fruit salad and its container (H48), confirmed the attempted poisoning with cyamemazine (H0) and hydrochloric acid (H48). In order to evaluate the anteriority of poisonings, hair analysis was requested and the medical records of the 6 previous months were also examined. Two 6-cm brown hair strands were sampled and the victim's medical record was seized in order to determine the treatments he had been given during the previous six months. Segmental hair testing on two 6-cm brown hair was conducted by GC-MS, LC-DAD and LC-MS/MS (0-2/2-4/4-6 cm; pg/mg). Haloperidol (9200/1391/227), amitriptyline (7450/1850/3260), venlafaxine (332/560/260), that had never been part of the victim's treatment were detected, as well as some benzodiazepines (alprazolam, bromazepam, nordazepam); cyamemazine was also detected in all the segments (9960/1610/2367) though only a single dose administration was reported in the medical records. The toxicological analyses performed at H0 and H48 confirmed the homicide attempts in the ICU. In addition, comparison of the results in hair analysis with the medical records confirmed repeated poisoning attempts over the previous six months, and thus explain the origin of the disorders presented by the victim. This case serves to remind us that repeated attempted murder can be difficult to diagnose and that hair analysis can be an effective way to detect such attempts.

Crystal Structures, X-Ray Photoelectron Spectroscopy, Thermodynamic Stabilities, and Improved Solubilities of 2-Hydrochloride Salts of Vortioxetine.

Two vortioxetine (VOT) salts with hydrochloride (VOT-HCl and VOT-0.5HCl) were prepared and structurally characterized. VOT-HCl features 1-dimensional P/M helical chains through N-H···Cl hydrogen bond interactions, whereas VOT-0.5HCl possesses a 1-dimensional zigzag structure in which 2 VOT molecules share a single proton through N···H+···N interactions. VOT-HCl converts into the monohydrate VOT-HCl·H2O after dissolution in water, whereas VOT-0.5HCl remains stable. The N 1s X-ray photoelectron spectroscopy analysis shows a characteristic binding energy peak at approximately 398.0 eV for VOT. The shift to high energy occurs at 400.3 eV for VOT-HCl and VOT-HBr, and at 399.7 eV for VOT-0.5HCl, which supports the salt formation by the degree of proton transfer and is confirmed by single-crystal X-ray analyses. The apparent equilibrium solubilities of VOT in water are significantly improved to 2.90 mg/mL (approximately a 32.0-fold increase over that of the free base) for VOT-HCl and to 0.59 mg/mL (approximately a 5.7-fold increase over that of the free base) for VOT-0.5HCl at 25°C.

A new online exhaust gas monitoring system in hydrochloric acid regeneration of cold rolling mills.

Measuring the content of hydrogen chloride (HCl) in exhaust gas used to take time and energy. In this paper, we introduce a new online monitoring system which can output real-time data to the monitoring center. The system samples and cools exhaust gas, and after a series of processing, it will be analyzed by a specific instrument. The core part of this system is remote terminal unit (RTU) which is designed on Cortex-A8 embedded architecture. RTU runs a scaled-down version of Linux which is a good choice of OS for embedded applications. It controls the whole processes, does data acquisition and data analysis, and communicates with monitoring center through Ethernet. In addition, through a software developed for windows, the monitoring process can be remotely controlled. The new system is quite beneficial for steel industry to do environment monitoring.

Laboratory investigation of three distinct emissions monitors for hydrochloric acid.

The measurement of hydrochloric acid (HCl) on a continuous basis in coal-fired plants is expected to become more important if HCl standards become implemented as part of the Federal Mercury and Air Toxics Standards (MATS) standards that are under consideration. For this study, the operational performance of three methods/instruments, including tunable diode laser absorption spectroscopy (TDLAS), cavity ring down spectroscopy (CRDS), and Fourier transform infrared (FTIR) spectroscopy, were evaluated over a range of real-world operating environments. Evaluations were done over an HCl concentration range of 0-25 ppmv and temperatures of 25, 100, and 185 °C. The average differences with respect to temperature were 3.0% for the TDL for values over 2.0 ppmv and 6.9% of all concentrations, 3.3% for the CRDS, and 4.5% for the FTIR. Interference tests for H2O, SO2, and CO, CO2, and NO for a range of concentrations typical of flue gases from coal-fired power plants did not show any strong interferences. The possible exception was an interference from H2O with the FTIR. The instrument average precision over the entire range was 4.4% for the TDL with better precision seen for concentrations levels of 2.0 ppmv and above, 2.5% for the CRDS, and 3.5% for the FTIR. The minimum detection limits were all on the order of 0.25 ppmv, or less, utilizing the TDL values with a 5-m path. Zero drift was found to be 1.48% for the TDL, 0.88% for the CRDS, and 1.28% for the FTIR. IMPLICATIONS: This study provides an evaluation of the operational performance of three methods/instruments, including TDL absorption spectroscopy (TDLAS), cavity ring down spectroscopy (CRDS), and FTIR spectroscopy, for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of temperature and no strong interferences for flue gases typical to coal-fired power plants. The results show that these instruments would be viable for the measurement of HCl in coal-fired plants if HCl standards become implemented as part of the Federal Mercury and Air Toxics Standards (MATS) standards that are under consideration.

Ranking of Molecular Biomarker Interaction with Targeted DNA Nucleobases via Full Atomistic Molecular Dynamics.

DNA-based sensors can detect disease biomarkers, including acetone and ethanol for diabetes and H2S for cardiovascular diseases. Before experimenting on thousands of potential DNA segments, we conduct full atomistic steered molecular dynamics (SMD) simulations to screen the interactions between different DNA sequences with targeted molecules to rank the nucleobase sensing performance. We study and rank the strength of interaction between four single DNA nucleotides (Adenine (A), Guanine (G), Cytosine (C), and Thymine (T)) on single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) with acetone, ethanol, H2S and HCl. By sampling forward and reverse interaction paths, we compute the free-energy profiles of eight systems for the four targeted molecules. We find that dsDNA react differently than ssDNA to the targeted molecules, requiring more energy to move the molecule close to DNA as indicated by the potential of mean force (PMF). Comparing the PMF values of different systems, we obtain a relative ranking of DNA base for the detection of each molecule. Via the same procedure, we could generate a library of DNA sequences for the detection of a wide range of chemicals. A DNA sensor array built with selected sequences differentiating many disease biomarkers can be used in disease diagnosis and monitoring.

Improvement of the ultra-trace voltammetric determination of Rh in environmental samples using signal transformation.

Rhodium (Rh) is present at the Earth's surface at ultra-trace concentrations (0.06 ng g(-1)); however, its use in catalytic converters has increased its deposition nearby traffic pressure and therefore the interest in analytical techniques for Rh determination has raised in the recent years. In this study we propose an improvement of Rh measurement by adsorptive voltammetry applying second-derivative signal transformation. The optimization of experimental parameters affecting the voltammetric analysis were carried out using sediment samples; these include the amount of sample digest used, the hydrochloric acid and formaldehyde concentrations, deposition potential and equilibration time. The use of the second derivative transformation provided well-defined peaks due to the minimization of background interferences, leading to a significant decrease in the detection limits. Accordingly, a detection limit of 200 fM Rh in the cell was obtained, which corresponds to 14 pg g(-1) of Rh for 200mg of sediments. The optimized methodology was applied to the analysis of Rh in a sediment core collected close to a motorway bridge from Tagus Estuary (Lisbon, Portugal). Here, Rh concentrations ranged from 0.06 to 0.47 ng g(-1), showing a surface Rh-enrichment linked to traffic, which was consistent with a Pt superficial peak. Reference materials were also analyzed, including road dust (BCR-723) and river sediment (JSD-2), and values obtained were in agreement with certified concentrations and previously values reported in the literature.

Protonation effect on ligands in EuL: a luminescent switcher for fast naked-eye detection of HCl.

A new luminescent coordination polymer, EuH(L)(2)(NO(3))(2) (EuL, HL = 2-(2-pyridin-2-yl)quinoline-4-carboxylic acid), has been solvothermally synthesized, and its framework of uncoordinated pyridyl rings was exploited for the binding and specific sensing of HCl via a protonation effect. The protonation effect changes the energy of the excited state of the ligands, rendering them unable to act as efficient antennae for Eu(3+) characteristic emission. Thus, we have developed a new, fast and convenient sensor for HCl, a gas harmful for the environment.

Sensitivity enhancement of pH indicator and its application in the evaluation of fish freshness.

The sensitivity of pH indicators is always confined in acidic solvents used during the immobilization because of the large deviation from their color transition points. By regulating the pH of indicators using organic acid or base, the color transition points of indicators could be readily achieved and the sensitivity could be greatly enhanced. In this study, bromophenol blue was selected as an example to interpret this improvement. And Hue, Saturation and Value (HSV) color model was applied to obtain digital color information of pH indicators. In addition, other two kinds of pH indicators were chosen and regulated to their color transition points as well. The resultant indicators together with the original ones were composed to a colorimetric sensor array and utilized to determine fish freshness. Compared with the original indicators, much higher sensitivity in the detection of fish freshness was obtained by the pH regulated indicators.