Fluorescent composite beads: An advanced tool for environmental monitoring and harmful pollutants removal from water.

The quality and safety of water sources have been significantly impacted by various pollutants, including trace elements. To address this concern, this study utilized composite beads made of alginate and carbon quantum dots (CDs) for detecting and removing As(III) and Se(IV) ions in tap water. Fluorescent CDs were hydrothermally synthesized and incorporated into an alginate-Ca2+ matrix through a straightforward procedure. Characterization analyses revealed distinct properties of the composite beads, containing varying amounts of CDs, compared to the pristine beads. Optimal adsorption parameters (30 mg of adsorbent, 10 mg/L of initial pollutant concentration, 35 °C, and 180 min of contact time) for the beads containing 30 w/w-% of CDs (Alg@CDs30) were determined through a fractional factorial design. These composite beads exhibited the highest adsorption capacity for both metals, achieving a removal rate of 94.5% for As(III) and 98.0% for Se(IV) in tap water. Kinetic and isothermal analyses indicated that the adsorption of both metals on Alg@CDs30 involves a combination of chemisorption and diffusion processes. Recycling experiments demonstrated that the composite beads could be reused up to 20 times without a noticeable loss of adsorption efficiency. Regarding the sensing property, our experiments revealed a significant reduction in the fluorescence emission intensity of Alg@CDs30 upon interaction with As(III) and Se(IV), confirming its ability to detect both ions in tap water, with limits of detection (LOD) of 2.6 ± 0.5 µg/L for As(III) and 1.1 ± 0.2 µg/L for Se(IV). The alginate-Ca2+ matrix s contributed to the stability of the CDs' fluorescence. These results confirm the potential of Alg@CDs beads as effective tools for the simultaneous monitoring and removal of hazardous metal ions from real water samples.

Composite hydrogel based on alginate-g-poly(acrylamide)/carbon nanotubes for solid phase extraction of metals from corn cereal samples.

Composite hydrogels containing nanofillers are extensively applied in the sorption of different compounds from aqueous solutions; however, this ability is poorly exploited in the extraction and pre-concentration of analytes from complex matrices. As a contribution to this field, this study reports the synthesis of a composite hydrogel of alginate-g-poly(acrylamide) matrix filled with functionalized multi-walled carbon nanotubes (ALG-g-PAAM/MWCNT-f). This composite served as a solid-phase extractor (SPE) for the separation of Pb2+ and Cd2+ ions from a digested corn cereal sample before their analytical determination. After composite characterization, a series of experiments using low dosages of ALG-g-PAAM/MWCNT-f demonstrated that the composite has a higher sorption capacity for Pb2+ (5.1 mg/g) and Cd2+ (3.9 mg/g) under favorable experimental conditions. As demonstrated, the presence of the MWCNT-f benefited the SPE performance of the composite. The sorption of both cations followed the pseudo-first order kinetics, while the experimental data were well-fitted by the Freundlich isotherm. Also, ALG-g-PAAM/MWCNT-f showed selectivity for Pb2+, and it is reusable up to 10 times without losing sorption performance. After sorption and extraction, both metals were completely recovered, facilitating their quantification by the MIP OES technique. In short, ALG-g-PAAM/MWCNT-f was an effective SPE for the separation and extraction of Pb2+ and Cd2+, which can be beneficial for food control and safety.

Combined computational and experimental study about the incorporation of phosphorus into the structure of graphene oxide.

Phosphorus-containing graphene-based hybrids are materials with outstanding properties for diverse applications. In this work, an easy route to produce phosphorus-graphene oxide hybrid materials is described, involving the use of variable amounts of H3PO4 and H2SO4 during the reaction of oxidation of a graphitic precursor. The physical and chemical features of the hybrids change significantly with the variation in the acid amounts used in the syntheses. XPS and solid-state 13C and 31P NMR results show that the hybrids contain large amounts of oxygen functional groups, with the phosphorus incorporation proceeding mostly through the formation of phosphate-like linkages and other functions with C-O-P bonds. The experimental findings are supported by DFT calculations, which allow the assessment of the energetics and the geometry of the interaction between phosphate groups and graphene-based models; these calculations are also used to predict the chemical shifts in the 31P and 13C NMR spectra of the models, which show good agreement with the experimentally observed solid-state NMR spectra.

Stable dark pulses produced by a graphite oxide saturable absorber in a fiber laser cavity.

In this paper, we report for the first time, to the best of our knowledge, the experimental generation of dark pulses in the 1.5 µm band from a passively $Q$Q-switched fiber laser employing graphite oxide as the saturable absorber, generating tunable microsecond pulses with kHz repetition rates. The graphite oxide samples were obtained by recycling the graphite present in Li-ion batteries used in cell phones through a chemical separation and oxidation process. Sample characterization employing x-ray diffraction, solid-state $ ^{{13}}{\rm C} $13C nuclear magnetic resonance, and Raman spectroscopy showed that the produced graphite oxide exhibited a homogeneously oxidized structure. Dark pulse emission could be observed at a relatively low pump threshold of 35 mW in a short 20 m laser cavity, indicating that the graphite oxide acted as a saturable absorber, significantly enhancing the nonlinearity of the laser cavity. Additionally, dark pulse operation was demonstrated at a high stability with a signal-to-noise ratio of 56 dB and a pulse-to-pulse timing jitter of 159.84 fs.

Recovery of latent fingermarks from brass cartridge cases: Evaluation of developers, analysis of surfaces and internal ballistic effects.

A study was undertaken wherein different fingermark developers were evaluated for the recovery of fingermarks from brass cartridge cases, besides the evaluation of factors such as firing effects and surface characterization of the cases. The latent fingermarks on α-brass plates, fired and unfired cartridge cases were deposited and aged for 1-14days before development with different developers. In order to mimic the fired cartridge case conditions, the brass plates were heated and examined at room temperature (RT), at 63 and at 200°C. The sequential treatment with cyanoacrylate, gun blue and fluorescent dye has been found to be the best among other developers for the recovery of latent fingermarks on brass surfaces including fired and unfired cartridge cases. Cartridge cases and other brass surfaces were also analyzed by surface characterization methods, including X-ray diffraction, scanning electronic microscopy, energy dispersive X-ray spectroscopy and metallographic examination. The tested surfaces correspond to α-phase brass Cu0.7Zn0.3 composition and have shown different surface morphologies (such as grain structure) and different levels of oxidation, even for cartridge cases obtained from the same batch. Due to this, the effectiveness of a given reagent for a specific brass surface is uncertain. Therefore, the application of the entire tested sequence of developers is strongly recommended. Further, the effects of firing on fingermarks on cartridge cases were examined, and the results indicated that the blowback of hot gases through the looseness between cartridge case and chamber wall of the firearm is the main cause responsible for deterioration of fingermarks during firing. Despite the recognized damage caused to fingermarks by the firing effects, good quality fingermarks were recovered from fired cartridge cases in which full fingermarks were intentionally deposited prior to firing. This indicates that the handling of the cartridges before and during the loading of the gun may have a strong influence on the quantity and quality of fingermarks, and that the firing itself is not the main responsible factor for the absence or low quality of fingermarks, as frequently reported in fired cartridge cases studies.

Ultrasound-assisted vapor generation of mercury.

Cold vapor generation arising from reduction of both Hg(2+) and CH(3)Hg(+) occurs using ultrasonic (US) fields of sufficient density to achieve both localized heating as well as radical-based attack in solutions of formic and acetic acids and tetramethylammonium hydroxide (TMAH). A batch sonoreactor utilizing an ultrasonic probe as an energy source and a flow through system based on a US bath were optimized for this purpose. Reduction of CH(3)Hg(+) to Hg(0) occurs only at relatively high US field density (>10 W cm(-3) of sample solution) and is thus not observed when a conventional US bath is used for cold vapor generation. Speciation of mercury is thus possible by altering the power density during the measurement process. Thermal reduction of Hg(2+) is efficient in formic acid and TMAH at 70 degrees C and occurs in the absence of the US field. Room temperature studies with the batch sonoreactor reveal a slow reduction process, producing temporally broad signals having an efficiency of approximately 68% of that arising from use of a conventional SnCl(2) reduction system. Molecular species of mercury are generated at high concentrations of formic and acetic acid. Factors affecting the generation of Hg(0) were optimized and the batch sonoreactor used for the determination of total mercury in SLRS-4 river water reference material.

Determination of total mercury and methylmercury in biological samples by photochemical vapor generation.

Cold vapor atomic absorption spectrometry (CV-AAS) based on photochemical reduction by exposure to UV radiation is described for the determination of methylmercury and total mercury in biological samples. Two approaches were investigated: (a) tissues were digested in either formic acid or tetramethylammonium hydroxide (TMAH), and total mercury was determined following reduction of both species by exposure of the solution to UV irradiation; (b) tissues were solubilized in TMAH, diluted to a final concentration of 0.125% m/v TMAH by addition of 10% v/v acetic acid and CH(3)Hg(+) was selectively quantitated, or the initial digests were diluted to 0.125% m/v TMAH by addition of deionized water, adjusted to pH 0.3 by addition of HCl and CH(3)Hg(+) was selectively quantitated. For each case, the optimum conditions for photochemical vapor generation (photo-CVG) were investigated. The photochemical reduction efficiency was estimated to be approximately 95% by comparing the response with traditional SnCl(2) chemical reduction. The method was validated by analysis of several biological Certified Reference Materials, DORM-1, DORM-2, DOLT-2 and DOLT-3, using calibration against aqueous solutions of Hg(2+); results showed good agreement with the certified values for total and methylmercury in all cases. Limits of detection of 6 ng/g for total mercury using formic acid, 8 ng/g for total mercury and 10 ng/g for methylmercury using TMAH were obtained. The proposed methodology is sensitive, simple and inexpensive, and promotes "green" chemistry. The potential for application to other sample types and analytes is evident.

Determination of mercury in biological samples by cold vapor atomic absorption spectrometry following cloud point extraction with salt-induced phase separation.

Method development for the pre-concentration of mercury in human hair, dogfish liver and dogfish muscle samples using cloud-point extraction and cold vapor atomic absorption spectrometry is demonstrated. Before the extraction, the samples were submitted to microwave-assisted digestion in a mixture of H(2)O(2) and HNO(3). Cloud point extraction was carried out using 0.5% (m/v) ammonium O,O-diethyldithiophosphate (DDTP) as the chelating agent and 0.3% (m/v) Triton X-114 as the non-ionic surfactant. Phase separation was induced after the addition of Na(2)SO(4) to a final concentration of 0.2 mol L(-1). Aliquots of the final extract were transferred to PTFE tubes and NaBH(4) and HCl were added. The mercury vapor was driven to a non-heated quartz tube for measuring the absorbance. The results obtained with salt-induced phase separation were in good agreement with the certified values at a 95% confidence level. An enrichment factor of 10 allowed a detection limit of 0.4 ng g(-1) to be obtained, which demonstrates the high sensitivity of the proposed procedure for the determination of mercury at trace levels.