Cold Vapor Atomic Fluorescence Spectrometry Research Articles

Health risk assessment for human mercury exposure from Cinnabaris-containing Baizi Yangxin Pills in healthy volunteers Po administration

BackgroundCinnabaris (α-HgS), a mineral traditional Chinese material medica, has been used in combination with other herbs manifesting some definite therapeutic effects for thousands of years. But the currently reported mercury poisoning incidents raised the doubts about the safety of Cinnabaris-containing traditional Chinese medicines (TCMs). Baizi Yangxin Pills (BZYXP) is a Cinnabaris-containing TCM widely used in clinical practice. This study evaluated the health risk of mercury exposure from BZYXP in healthy volunteers based on the total mercury and mercury species analysis of blood and urine after single and multiple doses of BZYXP. MethodsBlood pharmacokinetics and urinary excretion studies of mercury were compared between single (9 g, once daily) and multiple doses (9 g, twice daily, continued for 7 days) of BZYXP. The whole blood and urine samples were collected at the specific points or periods after the administration of BZYXP. The total mercury and mercury species in blood and urine samples were determined by cold vapor-atomic fluorescence spectrometry (CV-AFS) and HPLC-CV-AFS, respectively. ResultsThe mercury was excreted slowly and accumulated obviously after continuous exposure of BZYXP. Moreover, the well-known neurotoxin methylmercury (MeHg) was detected in blood samples after 7 days’ administration of BZYXP. In the urine samples, only Hg(II) was detected. Therefore, long-term use of BZYXP will cause mercury poisoning due to mercury's high accumulative properties and MeHg formation. ConclusionCinnabaris-containing TCMs such as BZYXP should be restricted to cases in which alternatives are available, and the blood mercury species profile should be monitored during the long-term clinical medication.

Local and landscape factors influencing mercury distribution in water, bottom sediment, and biota from lakes of the Araguaia River floodplain, Central Brazil

Mercury (Hg) is a chemical element widely present in the Earth's crust. However, its high toxicity and ability to accumulate in organisms and biomagnify through food chains characterize it as a global pollutant of primary control. We assessed total mercury concentrations ([THg]) in abiotic and biotic compartments from 98 floodplain lakes associated with the Araguaia River and six tributaries (Midwest Brazil). [THg] quantification in water was performed by cold vapor atomic fluorescence spectroscopy. [THg] in bottom sediment was assessed using cold vapor generation atomic absorption spectrophotometry, while [THg] in macrophyte, periphyton, and plankton were quantified by thermal decomposition atomic absorption spectrometry. Hotspots of [THg] in water, bottom sediment, and macrophytes were determined in areas impacted by pasture and urban areas. In contrast, hotspots of [THg] in periphyton and forest fires were determined in preserved areas downstream. [THg] in plankton did not show a clear spatial distribution pattern. The mean bioaccumulation factor order was plankton (2.3 ± 1.8) > periphyton (1.3 ± 0.9) > macrophytes (0.7 ± 0.4) (KW = 55.09, p < 0.0001). Higher [THg] in water and bottom sediment were associated with high pH (R2adj = 0.118, p = 0.004) and organic matter (R2adj = 0.244, p < 0.0001). [THg] in macrophytes were positively influenced by [THg] in water (R2adj = 0.063, p = 0.024) and sediment (R2adj = 0.105, p = 0.007). [THg] in periphyton are positively related to forest fires (R2adj = 0.156, p = 0.009) and [THg] in macrophytes (R2adj = 0.061, p = 0.03) and negatively related to lake depth (R2adj = 0.045, p = 0.02). The transfer of Hg from water and sediment to the biota is limited. However, the progressive increase of the bioaccumulation factor between macrophyte, periphyton, and plankton may indicate Hg biomagnification along the food chain of the Araguaia River floodplain.

The transformation of soil Hg oxidation states controls elemental Hg release in the greenhouse with applying organic fertilizer

The foliage vegetables cultivated in greenhouse of Hg-contaminated regions suffer from severe Hg contamination issues because of soil elemental Hg (Hg(0)) release. Application of organic fertilizer (OF) is the indispensable part of farming, but its influences on soil Hg(0) release are unclear. A new method of thermal desorption coupled with cold vapor atomic fluorescence spectrometry was developed to measure transformations of Hg oxidation states to elucidate the impact mechanism of OF on Hg(0) release process. Our results showed that the soil Hg(0) concentrations can directly determine its release fluxes. The application of OF causes that oxidizing reactions of Hg(0)/Hg(I) and Hg(I)/Hg(II) are excited; then soil Hg(0) concentrations decreases. Besides, the elevated soil organic matter by amending OF can complex with Hg(II), resulting in that the reductions of Hg(II) to Hg(I) and Hg(0) are inhibited. Additionally, the OF can directly adsorb soil Hg(0), decreasing the removability of Hg(0). Subsequently, the application of OF can significantly inhibit soil Hg(0) release, resulting in a pronounced decrease in interior atmospheric Hg(0) concentrations. Our results provide a novel perspective for enriching the fate of soil Hg that transformation of soil Hg oxidation states plays a crucial role in affecting soil Hg(0) release process.

Accumulation and distribution of mercury in agricultural soils, food crops and associated health risks: A case study of Shenda gold mine-Geita Tanzania

Contamination of the environment and foodstuff by potentially harmful elements (PHEs) has become a serious concern due to the associated health risks to the population. In the present study total mercury (Hg) levels in soil and food crops from farms around Shenda gold mine in Geita Tanzania was determined by Cold Vapor Atomic Fluorescence Spectrometry (CVAFS). Generally, it was found that there was significant different of Hg content in soil and food crops (P < 0.05) among studied sites. The total Hg concentrations determined were in the ranges of; soils (0.003-0.1220 mg/kg), rice (0.0752-0.1587 mg/kg) and vegetables (0.0556-0.3439 mg/kg) all measurement were based on dry weight basis (dw). Total Hg levels in soil were compared with the maximum allowable concentration (MAC) set by Tanzania Bureau of Standards (TBS) and United Kingdom (UK). All studied soil samples were within acceptable range (2 mg/kg) set by TBS and UK (1 mg/kg). Total Hg contents in food crop samples were compared with Chinese MAC of Hg (0. 01 and 0.02 mg/kg for leafy vegetables and grains respectively in a fresh weight basis). It was observed that Hg contents in potato leaves, pumpkin leaves and Chinese cabbage were within the MAC while Hg levels in cassava leaves and rice grains exceeded the MAC. In addition, Hg associated health risks to consumers of contaminated foods for residents around Shenda gold mine were estimated. The estimated weekly intake (EWI) of Hg due to consumption of rice grain was above the provisional tolerable weekly intake (PTWI) set by FAO/WHO (1.6 mg/kg bw/week) while the EWI due to consumption of leafy vegetables were below the PTWI. Target hazard quotient (THQ) was < 1 due to consumption of vegetables while THQ value for rice was >1, indicating a potential non-carcinogenic risk to adult population from the consumption of rice grain from the study area. Therefore, people living near Shenda goldmine might be potential victim of Hg accumulation in soil and food crops, thus necessary management options have to be in place.

Total mercury and fatty acids content in selected fish marketed in Quito - Ecuador. A benefit-risk assessment.

Total mercury and fatty acids contents were determined in muscles of croaker, snapper, dolphinfish, blue marlin, and shark, from different markets in the Metropolitan District of Quito, Ecuador. Fifty-five samples were collected and analyzed for total mercury using cold vapor atomic fluorescence spectrometry, and the fatty acids were analyzed using gas chromatography equipped with a flame ionization detector. The lowest total mercury levels were found in snapper [0.041µg·g-1 wet weight (ww)] while blue marlin showed the highest (5.883µg·g-1 ww). EPA +DHA ranged from 1.0mg·g-1 in snapper to 2.4mg·g-1 in shark. A high omega-3/omega-6 ratio was found for all fish types; however, the HQEFA for the benefit-risk ratio was above 1, suggesting an evident risk to human health. Based on our results, consumption of croaker and dolphinfish is recommended up to one serving per week, considering the importance of EFAs intake and avoiding fish with elevated MeHg content. Therefore, Ecuadorian authorities could enhance public standards for seafood safety and develop consumer advice for pregnant women and young children to determine good fish choices or those to avoid.

Functionalized graphene quantum dots obtained from graphene foams used for highly selective detection of Hg2+ in real samples

Here we report the use of graphene quantum dots (GQDs), obtained from 3D graphene foam, functionalized with 8-hydroxyquinoline (8-HQ) for the sensitive and selective detection of Hg2+ via front-face fluorescence. The great surface area and active groups within the GQDs permitted the functionalization with 8-HQ to increase their selectivity toward the analyte of interest. The fluorescence probe follows the Stern-Volmer model, yielding a direct relationship between the degree of quenching and the concentration of the analyte. Diverse parameters, including the pH and the use of masking agents, were optimized in order to improve the selectivity toward Hg2+ down to a limit of detection of 2.4 nmol L−1. It is hereby demonstrated that the functionalized GQDs work perfectly fine under adverse conditions such as acidic pH and in the presence of a large number of cationic and anionic interferences for the detection of Hg2+ in real samples. Parallel measurements using cold vapor atomic fluorescence spectrometry also demonstrated an excellent correlation with the front-face fluorescence method applied here for real samples including tap, river, underground, and dam waters.

Description of a Dimethylmercury Automatic Analyzer for the High-Resolution Measurement of Dissolved Gaseous Mercury Species in Surface Ocean Waters.

Our understanding of the significance of dimethylmercury (DMHg) to the mercury (Hg) global ocean biogeochemical cycle is unclear because of the lack of detailed DMHg measurements in the water column. To our knowledge, 30 years of published studies have generated no more than 200 DMHg data points in the ocean surface waters and marine boundary layer (MBL). To improve the precision and reduce the uncertainty in determining DMHg in surface seawater, we developed a simple and robust DMHg automatic analyzer (DAA). This DAA system couples the main sampling and analytic steps, including a continuous flow chamber, with dual Carbotrap preconcentration, a gas chromatographic column, a cold vapor atomic fluorescence spectrometry, and a data logger for signal integration. We compared the operation, performance, and reproducibility between our DAA and the traditional manual analytic method. Its advantages include the ease of operation, the high time resolution and precision (30 min sampling and <5% relative variation), and long-term stability (2 weeks). The DAA can determine DMHg in both the MBL and surface seawater. The estimated detection limits for DMHg with the DAA in the atmosphere and in surface seawater are 10 pg/m3 and 0.2 fM, respectively. The successful DAA field measurement in coastal waters indicates that it can help detect the low DMHg concentration in surface seawater, and the time series DMHg data helped our understanding of the DMHg behavior (sources and sinks) and its flux into the MBL. The comparison of DMHg concentration in various oceans also suggests that the coastal region had the lowest averaged DMHg, up to an order of magnitude lower than other ecosystems.

Mercury in Dried Market Fish of Hong Kong and San Francisco: Human Health Implications

Asian, Asian Pacific Islanders, and Asian American residents of San Francisco have higher exposure to mercury and the associated health risks associated with methylmercury toxicity from fish consumption than other demographics across the United States. Due to their higher annual fish consumption, Hong Kong Chinese residents have elevated risks to methylmercury exposure. Objectives: We investigate samples of dried market fish from San Francisco and from Hong Kong as potential sources of mercury contamination in fish commonly consumed by Asian and Asian American residents. Methods: We analyze 81 samples of dried market fish from San Francisco and Hong Kong for mercury concentration using Inductively Coupled Plasma Emission Spectrograph and Processing Cold Vapor Atomic Fluorescence Spectrometry. We binned into market categories, trophic level, and habitat type for statistical analysis. Results: No significant difference was observed in the mercury levels of samples between San Francisco and Hong Kong (p-value = 0.47). Dried samples did show higher rates of mercury than wet samples reported by the FDA. Data from dried market fish samples also show evidence of bioaccumulation: the concentration of toxins in higher trophic levels of fish (p-value &lt; 0.01). Eliminating apex predators, nearly all samples of fish from both locations and from lower trophic levels had levels below the lowest health advisory thresholds of 0.5 ppm methylmercury by weight. Discussion: Dried fish samples from markets in San Francisco and Hong Kong showed mercury levels with the potential to exceed guidelines set by the EPA and the EFSA, but consumption rates are lacking to know if this threshold is actually being exceeded by consumers. We make recommendations regarding the health risks of dried market fish and of consuming or avoiding fish from certain trophic groups.

Composition of trace residues from the contents of 11th-12th century sphero-conical vessels from Jerusalem.

The residues from the internal surface of four archaeological ceramic sherds, excavated from the Armenian Gardens, Jerusalem were analysed to characterise the contents of the original vessel. The sherds derive from four small, thick-walled, sphero-conical vessels recovered from a destruction layer, dating between the 11th and 12th century, Jerusalem. The residue has been analysed using light microscopy, biochemical characterisation, gas chromatography mass spectroscopy, inductively coupled plasma atomic emission spectroscopy and cold vapour atomic fluorescence spectrometry. This analysis established the presence of various compounds including fatty acids and notable levels of mercury, sulphur, aluminium, potassium, magnesium, nitrates and phosphorous. The contents and probable functions of the four vessels were characterised from the residues on these sherds as different from each other, reflecting their different decoration, manufacture and ceramic typologies. One of these vessels contains residue that indicate the vessel held oils. The residue of the second vessel is consistent with either scented materials or medicinal contents, while a third probably contained medicinal material. The unique fourth sherd is from a stoneware sphero-conical vessel with very thick walls, no decoration and the residue supports the possibility it was used for the storage of chemicals or may have held the chemical ingredients for an explosive device, consistent with a medieval grenade. This residue analysis of Mamluk sphero-conical vessels provides insight into luxury items, medicines, technology and trade in medieval Jerusalem.

Mercury speciation in estuarine water using dithiol-based magnetic solid-phase extraction and cold vapor atomic fluorescence spectrometry

In this work, a method for mercury speciation using magnetic nanoparticles (MNPs) coated with dithiol and detection by cold vapor atomic fluorescence spectrometry (CV AFS) was developed. The magnetic Fe3O4 nanoparticles were coated with Al2O3 and sodium dodecyl sulfate (SDS) and functionalized with 1,3,4-thiadiazole-2,5-dithiol (TDT). The resulting functionalized MNPs (FMNPs, Fe3O4@Al2O3-TDT) were dispersed in the water samples, and the sorption performance with different mercury species was investigated. Once retained on the surface of Fe3O4@ Al2O3-TDT MNPs, the mercury species were magnetically separated from the sample and eluted with HCl. The organic mercury species were oxidized employing KBr-KBrO3 (100 and 17 mM, respectively) in an acid medium (HCl 1.0 M), and the results were expressed considering the total inorganic mercury concentration. It was successfully applied in mercury speciation analysis in the estuarine water, followed by CV AFS determination. In the proposed method under optimal conditions (pH 6), inorganic mercury was quantified in a linear range from 10 to 2000 ng L−1, with a limit of detection of 0.55 ng L−1, relative standard deviation (RSD) < 1.62%, and an enrichment factor of twelve. The recoveries in spiked estuarine water samples ranged from 94 to 106% for Hg(II), 85–91% for MeHg, 83–94% for EtHg, and 84–95% (PhHg) using two levels of concentration (100 and 500 ng L−1). The method is accurate, precise, and efficiently applied in mercury species determination in a complex matrix without laborious and time-consuming sample preparation.

Simple Acid Digestion Procedure for the Determination of Total Mercury in Plankton by Cold Vapor Atomic Fluorescence Spectroscopy.

Plankton, at the bottom of the food web, play a central role in the entry of mercury into the aquatic biota. To investigate their role in mercury uptake, reliable analytical procedures for Hg analysis are highly sought. Wet digestion procedures for determining total mercury in different biological matrices have been established since years, however only few studies focused on planktonic samples. In the present work, a simple and cost-effective wet digestion method was developed for the determination of total mercury in samples of small plankton material using a cold vapor atomic fluorescence spectroscopy (CVAFS). The optimization of the digestion method was achieved by using glass vessels with Teflon caps, low amount of acids (3 mL w/w 65% HNO3 or 3 mL 50% v/v HNO3), a constant temperature of 85 °C, the presence and absence of pre-ultrasound treatment, and a continuous digestion period (12 h). Certified reference materials IAEA-450 (unicellular alga Scenedesmus obliquus) and BRC-414 (plankton matrix) were used to optimize and validate the digestion method. The recovery efficiency of the proposed method for IAEA-450 and BCR-414 (3.1 mg and 21.5 mg) ranged between 94.1 ± 7.6% and 97.2 ± 4.6%. The method displayed a good recovery efficiency and precision for plankton matrices of low size. Thus, allowing better digestion of planktonic samples for mercury analysis using CVAFS techniques.

Role of Ester Sulfate and Organic Disulfide in Mercury Methylation in Peatland Soils.

We examined the composition and spatial correlation of sulfur and mercury pools in peatland soil profiles by measuring sulfur speciation by 1s X-ray absorption near-edge structure spectrocopy and mercury concentrations by cold vapor atomic fluorescence spectroscopy. Also investigated were the methylation/demethylation rate constants and the presence of hgcAB genes with depth. Methylmercury (MeHg) concentration and organic disulfide were spatially correlated and had a significant positive correlation (p < 0.05). This finding is consistent with these species being products of dissimilatory sulfate reduction. Conversely, a significant negative correlation between organic monosulfides and MeHg was observed, which is consistent with a reduction in Hg(II) bioavailability via complexation reactions. Finally, a significant positive correlation between ester sulfate and instantaneous methylation rate constants was observed, which is consistent with ester sulfate being a substrate for mercury methylation via dissimilatory sulfate reduction. Our findings point to the importance of organic sulfur species in mercury methylation processes, as substrates and products, as well as potential inhibitors of Hg(II) bioavailability. For a peatland system with sub-μmol L-1 porewater concentrations of sulfate and hydrogen sulfide, our findings indicate that the solid-phase sulfur pools, which have a much larger sulfur concentration range, may be accessible to microbial activity or exchanging with the porewater.

Field determination of inorganic mercury in seawaters by a portable dual-channel and purge-and-trap system with atomic fluorescence spectrometry

ABSTRACT An on-line flow injection mercury analyser (FIMA) for inorganic mercury (Hg) analysis in environmental waters is presented. The FIMA is a portable dual-channel and purge-and-trap system combining aqueous reduction with stannous chloride (SnCl2), two-stage gold (Au) amalgamation, thermal desorption of Hg0 and final detection with cold vapour atomic fluorescence spectrometry (CVAFS). Simultaneous on-line operations of sample loading and analysis make analytical throughput and accuracy improved and contamination eliminated. Results of system optimisation and reliability regarding the determination of inorganic Hg2+ are described. Analytical performances of both channels were the same in terms of data reliability. Low procedural blanks were obtained from laboratory and field trip (≤5 pg, n = 30). Excellent calibrations (r2 > 0.99) with a high precision and good stability (RSD <5%, n = 30) were obtained. Detection limits and reproducibility of the methods have been estimated as ≤0.05 ng L−1 and <5% (0.5 ng L−1, n = 30). The system was finally validated by measurements comparison of the two channels (r2 > 0.98), and analysis of a certified reference material (coastal seawater BCR-579, recoveries 101 ± 4%, n = 10). Overall, a sample throughput of ~10 samples per hour with two-channel detections of FIMA can be achieved. The onboard analysis of inorganic Hg species (e.g. elemental, reactive, and total Hg) in surface seawaters of the East China Sea (ECS) are also successfully achieved. The portable FIMA is fast, easy, and robust for reliable monitoring of Hg in natural seawaters.

An Analytical Method for the Biomonitoring of Mercury in Bees and Beehive Products by Cold Vapor Atomic Fluorescence Spectrometry.

Bees and their products are useful bioindicators of anthropogenic activities and could overcome the deficiencies of air quality networks. Among the environmental contaminants, mercury (Hg) is a toxic metal that can accumulate in living organisms. The first aim of this study was to develop a simple analytical method to determine Hg in small mass samples of bees and beehive products by cold vapor atomic fluorescence spectrometry. The proposed method was optimized for about 0.02 g bee, pollen, propolis, and royal jelly, 0.05 g beeswax and honey, or 0.1 g honeydew with 0.5 mL HCl, 0.2 mL HNO3, and 0.1 mL H2O2 in a water bath (95 °C, 30 min); samples were made up to a final volume of 5 mL deionized water. The method limits sample manipulation and the reagent mixture volume used. Detection limits were lower than 3 µg kg−1 for a sample mass of 0.02 g, and recoveries and precision were within 20% of the expected value and less than 10%, respectively, for many matrices. The second aim of the present study was to evaluate the proposed method’s performances on real samples collected in six areas of the Lazio region in Italy.

Metals and metalloids in green turtle hepatic tissue (Chelonia mydas) from Santos Basin, Brazil

Metal and metalloid concentrations in the liver tissue of green turtles (Chelonia mydas) stranded on the Brazilian coast (n = 506) were studied using inductively coupled plasma mass spectrometry and cold vapor atomic fluorescence spectrometry. The influences of occurrence registers (date and location) and biological characteristics (sex, age, and developmental stage) were assessed, as well as the temporal influences of oil exploration and production activities. The mean concentrations of Cd, Cu, Mn, Zn, and Hg were the highest reported for the liver of C. mydas on the Brazilian coast. The mean element concentrations followed the order: Cu > Zn > Cd > Mn > As > Hg > Mo > Pb > V > Ni > Ba > Cr. Further, significant differences (p < 0.05) were observed for Hg between the sexes (males > females) and for As, Cu, Pb, Mo, and V between young individuals and older individuals (≥11 years), suggesting a relationship between the dietary shift inherent to green turtle development. These results were corroborated by the curved carapace length (CCL) data, wherein individuals residing in coastal areas (CCL > 50 cm) presented higher concentrations of Cu, Pb, Mo, Zn, Ba, and V than those in the oceanic stage (CCL < 30 cm). The opposite pattern was observed for As and Hg. The influences of spatial autocorrelation (Moran Index) at a global scale and oil production activities on the element concentrations were not observed. However, five hotspots of high metal concentrations were identified via a local spatial autocorrelation (local indicator of spatial association), existing predominantly in a region of heavy anthropic activity within the sampling area. Further, baseline element concentrations were established at the 95% confidence level. Overall, the developmental stage, which is related to feeding habits, had an expressive influence on element concentrations.

Photoactive Titanium Dioxide Films with Embedded Gold Nanoparticles for Quantitative Determination of Mercury Traces in Humic Matter-Containing Freshwaters

Mercury detection in humic matter-containing natural waters is often associated with environmental harmful substances for sample preparation. Herein we report an approach based on photoactive titanium dioxide films with embedded gold nanoparticles (AuNP@TiO2 dipstick) for chemical-free sample preparation and mercury preconcentration. For this purpose, AuNPs are immobilized onto a silicon wafer and further covered with a thin photoactive titanium dioxide layer. The AuNPs allow the preconcentration of Hg traces via amalgamation, while TiO2 acts as a protective layer and, at the same time, as a photocatalyst for UV-C radiation-based sample pretreatment. Humic matter, often present in natural waters, forms stabile complexes with Hg and so hinders its preconcentration prior to detection, causing a minor recovery. This problem is solved here by irradiation during Hg preconcentration onto the photoactive dipstick, resulting in a limit of detection as low as 0.137 ng L−1 using atomic fluorescence spectrometry (AFS). A 5 min preconcentration step is sufficient to obtain successful recovery of Hg traces from waters with up to 10 mg L−1 DOC. The feasibility of the approach was demonstrated by the determination of Hg traces in Danube river water. The results show no significant differences in comparison with standard cold vapor-atomic fluorescence spectrometry (CV-AFS) measurements of the same sample. Hence, this new AuNP@TiO2 dipstick provides a single-step sample preparation and preconcentration approach that combines sustainability with high analytical sensitivity and accuracy.

Evaluation of Potentially Toxic Elements in Mundaú Lagoon (Maceió, AL-Brazil): Systematic Environmental Monitoring of Water and Food Quality

The Mundaú lagoon (Maceió, AL), besides being relevant socially, economically, and culturally, also in its surroundings, presents an intense anthropic occupation, characterized by a large population and the industrial activities presence. In this systematic environmental monitoring study (from 2017 to 2019), concentrations of Al, As, Bi, Cd, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Sn, V, and Zn in surface waters, and total Hg content in the bivalve Mytella charruana (sururu) were recorded, using cold vapor atomic fluorescence spectrometry (or hydride generation) (HG/CV AFS), inductively coupled plasma mass spectrometry (ICP-MS), and chronopotentiometry. In the water samples, the following elements presented concentrations above the values recommended by the National Council for the Environment (CONAMA), in μg L-1: Al (24.4 -2008), Cu (1.88‑13.03), Fe (84.9‑4107), Hg (&lt; 0.0069-2.92), Mn (10.65-200), Pb (192-1443) and Zn (121‑997), and therefore, the water was classified following the water pollution index (WPI), as highly impure and polluted. The Hg content in sururu, the main food in Mundaú lagoon, ranged from 0.036‑0.63 mg kg-1 (dry weight). Further, the chemometric evaluation of the data based on the principal component and correlation analysis suggested a chemical-defined profile at the different sampling points.

Determination of mercury (thimerosal) in vaccines using different oxidants and cold vapor atomic fluorescence spectrometry in dilute acids

A simple and fast method was developed for the determination of thimerosal (TH) in vaccines based on decomposition through the oxidizing systems of the organic mercury compound to inorganic mercury (Hgino) using CV AFS for detection.

Photoluminescent nanoprobes based on thiols capped CdTe quantum dots for direct determination of thimerosal in vaccines

CdTe quantum dots (CdTe QD) have been produced at different times of synthesis (1, 2, and 4 h) using thiols as capping agents: mercaptopropionic acid (MPA), mercaptosuccinic acid (MSA) and N-acetyl-l-cysteine (NAC) using water as a solvent. The produced CdTe QD were characterized by UV–vis and photoluminescence (PL) spectroscopy and showed a relationship among reflux time, size, and spectroscopic properties. CdTe QD were shown to interact with thimerosal (TM), an organic mercury compound, and the PL intensity was effectively quenched, characterizing an ON-OFF process. However, the NAC capped CdTe (CdTe-NAC) at 1 h presented the best sensitivity for TM determination. Under optimized conditions, a linear range from 0.1 to 1.0 μg mL−1 (0.25–2.5 μM) and a LOD of 26.6 μg L−1 (66.7 nM) were achieved. The influence of different mercuric species [Hg(II), methylmercury, ethylmercury, and phenylmercury], along with thiosalicylic acid (TSA), and other ionic species on the sensitivity of the method and the interaction mechanism between TM and CdTe-NAC have been discussed. The method was successfully applied for direct quantification of TM in vaccines, and the results were validated by cold vapor atomic fluorescence spectroscopy (CV AFS). Finally, the proposed method proved to be fast, sensitive, and simple for suitable use in vaccine quality control.

Photo-generation of mercury cold vapor mediated by graphene quantum dots/TiO2 nanocomposite: On line time-resolved speciation at ultra-trace levels

Mercury speciation was achieved using a nanocomposite, consisting of graphene quantum dots (GQDs) and TiO2 nanoparticles, to mediate photo-degradation of mercurial species into the Hg cold vapor detected by atomic spectrometry. Sample solution (containing Hg2+, CH3CH2Hg, and CH3Hg at hundreds of ng L−1) was placed in quartz tube containing formic acid solution (2% v/v) and microliter aliquot of GQDs/TiO2 nanocomposite dispersion (0.6 mg of nanocomposite). The tube was placed inside a photochemical reactor then, adapted to the mercury-dedicated spectrometer. Quantitative speciation was achieved taking advantage of the differences in UV photodegradation kinetics: Hg2+ (5 min), CH3CH2Hg (9 min) and CH3Hg (13 min). Gas-chromatography cold vapor atomic fluorescence spectrometry was used to confirm the evolution of the reactions over time during photo-reaction. The limits of detection were 10 ng L−1 for CH3CH2Hg and 7 ng L−1 for Hg2+ and CH3Hg.