An overview of automated flow systems for total and isotopic analysis of strontium and yttrium in samples of environmental interest.

Due to the different uses of radioactivity during the last decades, there has been an increase in the concentration of natural and artificial radionuclides in the environment. This, along with some accidents with a high affect public opinion (for example, Chernobyl and Fukushima), have led to the growth and establishment of environmental radioactivity monitoring programs. Currently, trends in legislation and research are focused on the development of accurate, precise, reliable and fast analytical methods with low limits of detection (LOD) for radionuclides determination, such as strontium and yttrium, in environmental samples. In this paper, two comprehensive reviews and four automated analytical systems for total and isotopic determination of yttrium and strontium are presented. The developed methods have been applied in the analysis of environmental samples with low concentrations of these analytes. These methodologies have been automated by exploiting flow analysis techniques, such as multi-syringe flow injection analysis (MSFIA), Sequential injection analysis (SIA) and laboratory-on-valve (LOV) systems, achieving a minimal handling and low consumption of samples and reagents, a significant reduction in waste generation and a high frequency of analysis. In the developed methodologies, some spectrometric methods such as ICP-OES and ICP-MS have been implemented as detection techniques instead of radiometric detectors obtaining a fully automated, low-cost and fast yttrium and strontium determinations.

Thiol-Functionalized MIL-100(Fe)/Device for the Removal of Heavy Metals in Water.

The preparation of a functional device based on a functionalized MIL-100(Fe) metal-organic framework for the solid-phase extraction of heavy metals is reported. By a simple and easy straightforward grafting procedure, a thiol-functionalized MIL-100(Fe) material (MIL-100(Fe)-SH) with a S/Fe ratio of 0.80 and a surface area of 840 m2 g-1 was obtained. MIL-100(Fe)-SH exhibited a higher Hg(II) extraction (96 ± 5%) than that of MIL-100(Fe) (78 ± 4%) due to the interaction between thiol groups and Hg(II) ions. For practical applications, the obtained MIL-100(Fe)-SH was integrated by a simple method to a 3D printed support based on a matrix of interconnected cubes using poly(vinylidene fluoride) as binder, obtaining a functional device that simultaneously acts as stirrer and sorbent. The developed device showed high efficiency for the removal of Hg(II), good reusability, and excellent performance for the simultaneous preconcentration and further detection and quantification of Hg(II), Pb(II), and As(V) in tap, well, and lake water samples.

Dynamics of Major and Trace Elements in Water-Soil-Tree Interaction: Translocation in Pyrus malus in Chihuahua, Mexico Using ICP-OES and Its Health Risk Implications.

The transference of metals from water irrigation and soil to plants is a possible pathway of contamination for the trophic chain. This research is focused on the distribution of 16 analytes in the water-soil-tree (Pyrus malus) interaction in an agricultural region in the state of Chihuahua in Mexico from August 2019 (first sampling) to August 2020 (second sampling). The apple variety under investigation was Golden Delicious; it was found that the trace elements of As (0.18-0.34 mg·kg-1) and Cd (0.11-0.14 mg·kg-1) in the apple were above the corresponding permissible limit, according to FAO/WHO, and Cr (0.08-0.86 mg·kg-1) was below the limit. Furthermore, the health risk implications were estimated by the Hazard Quotients (HQ) and carcinogenic risk (CR). For carcinogenic risk, As, Cd, and Cr exceeded the risk limit (CR > 10-4). This investigation as well provides a link for similar research around the globe. Major and trace elements detection was performed with the Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) technique, along with a prior homogenization of samples and microwave acid digestion. To obtain the statistical behavior, an analysis of variance and correlation was performed.

Automatic multicommuted flow systems applied in sample treatment for radionuclide determination in biological and environmental analysis.

The presence of artificial and natural radioactivity in the environment is currently a topic of great relevance and ecological interest, even in human health issue, due to the increase of different anthropogenic activities. The use of multicommuted flow analysis techniques (e.g. Multi-Syringe Flow Injection Analysis - MSFIA, Lab-On-Valve - LOV and Lab-In-Syringe - LIS) has allowed the automation of radiochemical procedures to separate and preconcentrate radionuclides in environmental and biological samples. In comparison with the manual approach commonly used in routine analysis for radioactivity monitoring, the automation has enabled the development of highly reproducible methodologies with a great analysis frequency. Moreover, during the analytical procedure, the intervention of the analyst is drastically reduced, minimizing the radiological risk. The automation also offers significant advantages such as minimum consumption of time and reagents, reducing the cost and the generation of waste, contributing to the green chemistry. In this review, several multicommuted flow analysis techniques (MSFIA, LOV and LIS) reported in the last decade applied for the development of automatic sample treatment methodologies, used to separate, preconcentrate and quantify 90Sr, 99Tc, natural U and 226Ra in biological and environmental samples are described and critically compared.

Fast-response flow-based method for evaluating 131I from biological and hospital waste samples exploiting liquid scintillation detection.

This paper presents a fast and automatic flow-based method to extract 131I from biological samples and hospital waste, previous to liquid scintillation detection. 131I is a radionuclide extensively used in Nuclear Medicine due to their beta and gamma disintegrations, whereby hospitals have to manage the associated waste generation. The automatic developed system is based on Lab-On-Valve (LOV) flow-technique exploiting Cl-resin (135 mg per extraction). This methodology allows performing sample extractions and measurements on the same day, since the extraction frequency takes 1.4-4 h-1, depending on the analysed sample volume, plus up to 2 h of measurement for each vial. 131I is retained as iodine ion and eluted with sodium sulphide 0.2 mol L-1. The maximum sample volume that can be preconcentrated is 20 mL, reaching an extraction efficiency of 85 ±â€¯5%. The minimum detectable activity (MDA) is 0.05 Bq, showing a precision of 7% RSD (n = 5). Both, biological samples (urine and saliva) and hospital waste samples can be satisfactorily analysed by the proposed system, obtaining recoveries between 90 and 110%. The developed method is then suitable to implement in hospitals, improving the surveillance of the 131I environmental release.

Direct photoimmobilization of extraction disks on "green state" 3D printed devices.

Post-curing is essential to improve the mechanical properties of 3D printed parts fabricated by stereolithography (SLA), since right after 3D printing they remain in a "green state". It means that the 3D printed parts have reached their final shape, but the polymerization reaction has not been yet completed. Herein, we take advantage of the tacky partially polymerized surface of "green state" SLA 3D printed parts to immobilize extraction disks and miniature magnets, which after UV post-curing, become permanently attached to the 3D printed part resulting in a rotating-disk sorptive extraction device (RDSE). The developed "stick & cure" procedure is reagent-free and does not require any additional preparation time, specialized skills, or instrumentation. As proof of concept, 3D printed RDSE devices with immobilized chelating disks have been applied to the simultaneous extraction of 14 trace metals prior to ICP-OES determination, featuring LODs between 0.03 and 1.27 µg L-1, and an excellent device-to-device reproducibility (n = 5, RSD = 2.7-8.3%). The developed method was validated using certified wastewater and soil reference samples, and satisfactory spiking recoveries were obtained in the analysis of highly polluted solid waste treatment plant leachates (89-110%). In addition, exploiting the versatility of 3D printing, nine RDSE devices with different shapes were fabricated. Their performance was evaluated and compared for the fast extraction of the highly toxic Cr (VI) as its 1,5-diphenylcarbazide complex in reversed-phase mode, showing different extraction performance on depending on the shape of the 3D printed RDSE device.

Culture-attenuated pathogenic Leptospira lose the ability to survive to complement-mediated-killing due to lower expression of factor H binding proteins.

Several pathogens including Gram-negative bacteria hijack complement regulators to escape host's innate response. Pathogenic Leptospira species bind Factor H, C4b binding protein and vitronectin from the complement system. We evaluated the ability of low passage (LP) and culture-attenuated (CA) pathogenic strains of Leptospira, to bind Factor H. We used LOCaS46 (Leptospira interrogans sv Canicola), LOVe30 (L. interrogans sv Icterohaemorrhagiae) and MOCA45 (L. santarosai sv Tarassovi), and ten high passage strains of Leptospira [used in the microscopic agglutination test (MAT)]. Afterwards, we assessed their survival in normal human serum (NHS). Interestingly, the ability in binding Factor H was higher for LOCaS46 and LOVe30 LP strains, than for the respective CA strains suggesting that the ability of evading the alternative complement pathway is lost after culture attenuation. Accordingly, the level of mRNA expression of the Factor H binding proteins, LigA, LigB and Lsa23 was higher in these LP strains than in the corresponding CA strains. Unexpectedly, no difference in Factor H binding and surviving was observed between LP and CA MOCA45 strains. The high passage MAT-reference strains showed variation in Factor H binding ability, but, in most cases, the ability for capturing Factor H by Leptospira strains correlated with their survival in NHS.

3D printed device for the automated preconcentration and determination of chromium (VI).

A 3D printed device for the fully automated disk-based solid-phase extraction (SPE) of Cr (VI) from water samples has been fabricated. The compatibility of the use of organic solvents for analyte elution with 3D printed flow devices based on polymers fabricated using stereolithograph​y has been evaluated. The developed methodology comprises the complexation of Cr (VI) with 1, 5-diphenylcarbazide (DPC) in acidic medium and the subsequent retention of the complex in a SBD-RPS disk contained within the 3D printed device. A multisyringe flow injection analysis system with online spectrophotometric detection has been used for the automation of the method. The fabricated 3D printed device integrates the different components of the flow analysis manifold, including connectors and mixers, being a powerful approach towards the reproducible construction of highly integrated flow-based manifolds. The extracted Cr (VI)-DPC complex is eluted with a mixture of methanol- sulfuric acid and quantified at 540 nm. The effect on the analytical signal and the optimization of variables were evaluated using multivariate and univariate techniques. A detection limit of 1 ng Cr (VI) and a linear working range of 3.2-600 ng Cr (VI) were obtained using a sample volume of 2 ml. The intra-day and inter-day RSDs were 4.8% (10 µg L-1, n = 12) and 3.4% (n = 5, different day with a different disk), respectively. The applicability of the fabricated 3D printed device has been proved by the determination of Cr (VI) in groundwater, surface water and leachates.

3D printed device including disk-based solid-phase extraction for the automated speciation of iron using the multisyringe flow injection analysis technique.

The development of advanced manufacturing techniques is crucial for the design of novel analytical tools with unprecedented features. Advanced manufacturing, also known as 3D printing, has been explored for the first time to fabricate modular devices with integrated features for disk-based automated solid-phase extraction (SPE). A modular device integrating analyte oxidation, disk-based SPE and analyte complexation has been fabricated using stereolithographic 3D printing. The 3D printed device is directly connected to flow-based analytical instrumentation, replacing typical flow networks based on discrete elements. As proof of concept, the 3D printed device was implemented in a multisyringe flow injection analysis (MSFIA) system, and applied to the fully automated speciation, SPE and spectrophotometric quantification of Fe in water samples. The obtained limit of detection for total Fe determination was 7ng, with a dynamic linear range from 22ng to 2400ng Fe (3mL sample). An intra-day RSD of 4% (n = 12) and an inter-day RSD of 4.3% (n = 5, 3mL sample, different day with a different disk), were obtained. Incorporation of integrated 3D printed devices with automated flow-based techniques showed improved sensitivity (85% increase on the measured peak height for the determination of total Fe) in comparison with analogous flow manifolds built from conventional tubing and connectors. Our work represents a step forward towards the improved reproducibility in the fabrication of manifolds for flow-based automated methods of analysis, which is especially relevant in the implementation of interlaboratory analysis.

Masking Agents Evaluation for Lead Determination by Flow Injection-Hydride Generation-Atomic Fluorescence Spectrometry Technique: Effect of KI, L-Cysteine, and 1,10-Phenanthroline.

Hydride generation (HG) of lead technique presents interferences from foreign ions of complex matrix samples. In order to minimize these interferences, the effect of masking agents such as KI, L-cysteine, and 1,10-phenanthroline was studied in the absence and in the presence of selected interfering species (As, Cr, Cu, and Fe). Different modes of addition of masking agents were accomplished, that is, to either sample or KBH4 reducing solution. The lead determinations were performed using a flow injection analysis (FIA) system coupled to HG and atomic fluorescence spectrometry (AFS). The linearity of calibration curves (1-10 µg Pb L(-1)) was not affected by the addition of the masking agents. The use of KI in the reducing solution diminished interferences from concentrations of As and Cu, while 1,10-phenanthroline showed a positive effect on the interference by As. Moreover, Cr and Cu appeared to be the most serious interfering ions for plumbane (PbH4), because they drastically reduced the analytical signal of lead. Fe did not present any interference under the employed experimental conditions, even at high levels. The accuracy was established through the analysis of certified reference material (i.e., BCR-610, groundwater) using KI as masking agent. The detection limit reached by FIA-HG-AFS proposed methodology was 0.03 µg Pb L(-1).

Automatic flow analysis method to determine traces of Mn²âº in sea and drinking waters by a kinetic catalytic process using LWCC-spectrophotometric detection.

A new automatic kinetic catalytic method has been developed for the measurement of Mn(2+) in drinking and seawater samples. The method is based on the catalytic effect of Mn(2+) on the oxidation of tiron by hydrogen peroxide in presence of Pb(2+) as an activator. The optimum conditions were obtained at pH 10 with 0.019 mol L(-1) 2'2 bipyridyl, 0.005 mol L(-1) tiron and 0.38 mol L(-1) hydrogen peroxide. Flow system is based on multisyringe flow injection analysis (MSFIA) coupled with a lab-on-valve (LOV) device exploiting on line spectrophotometric detection by a Liquid Waveguide Capillary Cell (LWCC), 1m optical length and performed at 445 nm. Under the optimized conditions by a multivariate approach, the method allowed the measurement of Mn(2+) in a range of 0.03-35 µg L(-1) with a detection limit of 0.010 µg L(-1), attaining a repeatability of 1.4% RSD. The method was satisfactorily applied to the determination of Mn(2+) in environmental water samples. The reliability of method was also verified by determining the manganese content of the certified standard reference seawater sample, CASS-4.

Estimation of seasonal risk caused by the intake of lead, mercury and cadmium through freshwater fish consumption from urban water reservoirs in arid areas of northern Mexico.

Bioavailability and hence bioaccumulation of heavy metals in fish species depends on seasonal conditions causing different risks levels to human health during the lifetime. Mercury, cadmium and lead contents in fish from Chihuahua (Mexico) water reservoirs have been investigated to assess contamination levels and safety for consumers. Muscle samples of fish were collected across the seasons. Lead and cadmium were analyzed by inductively coupled plasma-optical emission spectrometry, and mercury by cold-vapor atomic absorption spectrometry. The highest concentrations of cadmium (0.235 mg/kg), mercury (0.744 mg/kg) and lead (4.298 mg/kg) exceeded the maximum levels set by European regulations and Codex Alimentarius. Lead concentrations found in fish from three water reservoirs also surpassed the limit of 1 mg/kg established by Mexican regulations. The provisional tolerable weekly intake (PTWI) suggested by the World Health Organization for methyl mercury (1.6 µg/kg bw per week) was exceeded in the spring season (1.94 µg/kg bw per week). This might put consumers at risk of mercury poisoning.

The Alteration of Neonatal Raphe Neurons by Prenatal-Perinatal Nicotine. Meaning for Sudden Infant Death Syndrome.

Nicotine may link maternal cigarette smoking with respiratory dysfunctions in sudden infant death syndrome (SIDS). Prenatal-perinatal nicotine exposure blunts ventilatory responses to hypercapnia and reduces central respiratory chemoreception in mouse neonates at Postnatal Days 0 (P0) to P3. This suggests that raphe neurons, which are altered in SIDS and contribute to central respiratory chemoreception, may be affected by nicotine. We therefore investigated whether prenatal-perinatal nicotine exposure affects the activity, electrical properties, and chemosensitivity of raphe obscurus (ROb) neurons in mouse neonates. Osmotic minipumps, implanted subcutaneously in 5- to 7-day-pregnant CF1 mice, delivered nicotine bitartrate (60 mg kg(-1) d(-1)) or saline (control) for up to 28 days. In neonates, ventilation was recorded by head-out plethysmography, c-Fos (neuronal activity marker), or serotonin autoreceptors (5HT1AR) were immunodetected using light microscopy, and patch-clamp recordings were made from raphe neurons in brainstem slices under normocarbia and hypercarbia. Prenatal-perinatal nicotine exposure decreased the hypercarbia-induced ventilatory responses at P1-P5, reduced both the number of c-Fos-positive ROb neurons during eucapnic normoxia at P1-P3 and their hypercapnia-induced recruitment at P3, increased 5HT1AR immunolabeling of ROb neurons at P3-P5, and reduced the spontaneous firing frequency of ROb neurons at P3 without affecting their CO2 sensitivity or their passive and active electrical properties. These findings reveal that prenatal-perinatal nicotine reduces the activity of neonatal ROb neurons, likely as a consequence of increased expression of 5HT1ARs. This hypoactivity may change the functional state of the respiratory neural network leading to breathing vulnerability and chemosensory failure as seen in SIDS.

Uranium monitoring tool for rapid analysis of environmental samples based on automated liquid-liquid microextraction.

A fully automated in-syringe (IS) magnetic stirring assisted (MSA) liquid-liquid microextraction (LLME) method for uranium(VI) determination was developed, exploiting a long path-length liquid waveguide capillary cell (LWCC) with spectrophotometric detection. On-line extraction of uranium was performed within a glass syringe containing a magnetic stirrer for homogenization of the sample and the successive reagents: cyanex-272 in dodecane as extractant, EDTA as interference eliminator, hydrochloric acid to make the back-extraction of U(VI) and arsenazo-III as chromogenic reagent to accomplish the spectrophotometric detection at 655 nm. Magnetic stirring assistance was performed by a specially designed driving device placed around the syringe body creating a rotating magnetic field in the syringe, and forcing the rotation of the stirring bar located inside the syringe. The detection limit (LOD) of the developed method is 3.2 µg L(-1). Its good interday precision (Relative Standard Deviation, RSD 3.3%), and its high extraction frequency (up to 6 h(-1)) makes of this method an inexpensive and fast screening tool for monitoring uranium(VI) in environmental samples. It was successfully applied to different environmental matrices: channel sediment certified reference material (BCR-320R), soil and phosphogypsum reference materials, and natural water samples, with recoveries close to 100%.

Automated method for simultaneous lead and strontium isotopic analysis applied to rainwater samples and airborne particulate filters (PM10).

A new automated, sensitive, and fast system for the simultaneous online isolation and preconcentration of lead and strontium by sorption on a microcolumn packed with Sr-resin using an inductively coupled plasma mass spectrometry (ICP-MS) detector was developed, hyphenating lab-on-valve (LOV) and multisyringe flow injection analysis (MSFIA). Pb and Sr are directly retained on the sorbent column and eluted with a solution of 0.05 mol L(-1) ammonium oxalate. The detection limits achieved were 0.04 ng for lead and 0.03 ng for strontium. Mass calibration curves were used since the proposed system allows the use of different sample volumes for preconcentration. Mass linear working ranges were between 0.13 and 50 ng and 0.1 and 50 ng for lead and strontium, respectively. The repeatability of the method, expressed as RSD, was 2.1% and 2.7% for Pb and Sr, respectively. Environmental samples such as rainwater and airborne particulate (PM10) filters as well as a certified reference material SLRS-4 (river water) were satisfactorily analyzed obtaining recoveries between 90 and 110% for both elements. The main features of the LOV-MSFIA-ICP-MS system proposed are the capability to renew solid phase extraction at will in a fully automated way, the remarkable stability of the column which can be reused up to 160 times, and the potential to perform isotopic analysis.

Automated total and radioactive strontium separation and preconcentration in samples of environmental interest exploiting a lab-on-valve system.

A novel lab-on-valve system has been developed for strontium determination in environmental samples. Miniaturized lab-on-valve system potentially offers facilities to allow any kind of chemical and physical processes, including fluidic and microcarrier bead control, homogenous reaction and liquid-solid interaction. A rapid, inexpensive and fully automated method for the separation and preconcentration of total and radioactive strontium, using a solid phase extraction material (Sr-Resin), has been developed. Total strontium concentrations are determined by ICP-OES and (90)Sr activities by a low background proportional counter. The method has been successfully applied to different water samples of environmental interest. The proposed system offers minimization of sample handling, drastic reduction of reagent volume, improvement of the reproducibility and sample throughput and attains a significant decrease of both time and cost per analysis. The LLD of the total Sr reached is 1.8ng and the minimum detectable activity for (90)Sr is 0.008Bq. The repeatability of the separation procedure is 1.2% (n=10).

Diagnostic and treatment challenges for the pediatric hematologist oncologist in endemic areas for coccidioidomycosis.

Coccidioidomycosis is a mycosis endemic to certain areas in the Southwest, mostly Arizona and California, Mexico, and parts of Central and South America. Disseminated coccidioidomycosis is much more common in immunocompromised hosts; therefore, it is frequently encountered by pediatric oncologists in endemic areas. Special attention is needed to diagnose, effectively treat the infection, and appropriately adjust chemotherapy treatment plans to minimize immunosuppression. We describe the presentation and course of 6 patients with coccidioidomycosis who were seen by the pediatric hematology-oncology service at the University of Arizona during the last 3 years. Coccidioidomycosis is a relatively common infection encountered by pediatric oncologists in the southwestern states and should be considered in the differential diagnosis of patients living or visiting these areas.

[100 years after Kienböck's description: review of the etiology of Kienböck's disease from a historical perspective]. / 100 Jahre nach Kienböck: Literaturübersicht über die Ursachenforschung der Mondbeinnekrosen.

Kienböck's disease (KD) leads to collapse of the lunate bone with severe consequences for the wrist function which for some patients may result in occupational invalidity. The many synonyms of KD (aseptic necrosis or avascular necrosis) insinuate that the true etiopathology remains poorly understood. This reviews aims at exploring the level of evidence which brought forward the different hypotheses on the origin of KD. The widespread theories about the origin were formed about 100 years ago but a specific therapy is still not within reach. Although the cause of the disease remains essentially unknown it is officially recognized as an occupational disease in Germany. Empirical attempts to explain the etiopathology are based on compression of the lunate, impaired vascularity through vibration exposition, fracture and dislocation of the lunate from the radiolunate fossa. The level of evidence urges a cautious interpretation of currently discussed hypotheses on the etiology of KD.

Mercury levels in locally manufactured Mexican skin-lightening creams.

Mercury is considered one of the most toxic elements for plants and animals. Nevertheless, in the Middle East, Asia and Latin America, whitening creams containing mercury are being manufactured and purchased, despite their obvious health risks. Due to the mass distribution of these products, this can be considered a global public health issue. In Mexico, these products are widely available in pharmacies, beauty aid and health stores. They are used for their skin lightening effects. The aim of this work was to analyze the mercury content in some cosmetic whitening creams using the cold vapor technique coupled with atomic absorption spectrometry (CV-AAS). A total of 16 skin-lightening creams from the local market were investigated. No warning information was noted on the packaging. In 10 of the samples, no mercury was detected. The mercury content in six of the samples varied between 878 and 36,000 ppm, despite the fact that the U.S. Food and Drug Administration (FDA) has determined that the limit for mercury in creams should be less than 1 ppm. Skin creams containing mercury are still available and commonly used in Mexico and many developing countries, and their contents are poorly controlled.