Cold Vapor Atomic Fluorescence Research Articles

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.

Regionally representative hair mercury levels in Canadian First Nations adults living on reserves

ObjectiveThe primary objective of this participatory study was to assess the current body burden of mercury among First Nations adults.MethodsThe First Nations Food, Nutrition and Environment Study (2008–2018) collected regionally representative data from First Nations adults living on reserves south of the 60th parallel. Mercury was analyzed in hair as a preferred biomarker for prolonged exposure. Hair samples, a 5 mm bundle cut from the occipital region, were collected from the participants who gave consent and measured for total mercury concentrations using cold vapor atomic fluorescence spectrophotometry.ResultsIn total, 3404 First Nations adults living in 92 communities provided hair samples. This represents 52.5% of the respondents to the household surveys. The mean hair mercury concentrations were 0.56 μg/g among all participants and 0.34 μg/g among women of childbearing age (WCBA). There were 64 exceedances of Health Canada’s mercury biomonitoring guidelines (44 WCBA, 8 women aged 51+ years, 3 men aged 19–50 years, and 9 men aged 51+ years).ConclusionCurrent mercury exposure no longer presents a significant clinical health risk in most of the First Nations population south of the 60th parallel across Canada. However, mercury exposure continues to be an ongoing environmental public health concern that requires continued monitoring and assessment. Women of childbearing age (19–50 years) and older individuals living in northern ecozones and Quebec have higher mercury exposures, often exceeding Health Canada’s guidelines. Careful risk communication and risk management programs need to focus on northern ecozones and Quebec.

Mercury contamination at Vembanad Lake and near-shore regions in the southwest coast of India

Mercury (Hg) contamination in aquatic systems is a universal concern because of its persistence, bioaccumulation, toxicity, and trans-boundary nature. The current study focuses on monitoring the fate and transport of Hg in aquatic matrices such as water, interstitial water, sediment and fish in a tropical coastal ecosystem. The cold vapour atomic fluorescence spectrometer was used for the Hg analysis. The study assessed the fractionation of Hg and its methylation potential in sediments. The high Hg concentration in fish tissues showed the ineffectiveness of biogeochemical control over the methyl Hg mobility and bioavailability through the food web. Research results indicate that the accumulation potential of Hg subsequently increases along the food chain. The conducive physico-chemical environment at the sediment–water interface supports chemical transformations/transport of Hg from one matrix to the next. The fate of Hg in the lake has also been discussed based on the data generated.

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.

Total mercury in hair as biomarker for methylmercury exposure among women in central Sweden- a 23 year long temporal trend study.

Exposure to methylmercury (MeHg) through fish is a global public health problem. Exposure monitoring is essential for health risk assessment, especially in pregnant women and children due to the documented neurotoxicity. Herein, we evaluate a time series of MeHg exposure via fish in primiparous Swedish women, covering a time period of 23 years (1996-2019). The 655 included mothers were part of the POPUP study (Persistent Organic Pollutants in Uppsala Primiparas) conducted by the Swedish Food Agency (SFA). MeHg exposure was assessed via measurements of total mercury (Hg) in hair using either cold vapor atomic fluorescence spectrophotometry or inductively coupled plasma mass spectrometry, showing very good linear agreement (R2=0.97). Maternal characteristics and fish consumption were obtained via questionnaires. The median concentration of total Hg in hair was 0.38mg/kg (range 0.17-1.5) in 1996 and 0.25mg/kg (range 0.03-1.1) in 2019. On average the women consumed 11±8.2 meals of fish per month, and fish consumption was positively correlated with total Hg in hair (Spearman correlation: 0.39; p<0.001). In multiple regression analyses, the geometric mean annual decrease of total Hg in hair was-2.5% (95% CI: -3.2,-1.8%). Total fish consumption increased up to 2011 (B: 0.32 times/month per year; 95% CI 0.17, 0.46) after which it started to decline (B: -0.66 times/month per year; 95% CI -0.92,-0.40). Moreover, both total Hg in hair and fish consumption was positively associated with maternal age and education, and inversely associated with pre-pregnancy BMI. In conclusion, the exposure to MeHg via fish appears to be slowly declining among Swedish pregnant women.

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.

Optimization of a Digestion Method to Determine Total Mercury in Fish Tissue by Cold Vapor Atomic Fluorescence Spectrophotometry.

Several microwave-assisted digestion methods were tested at the Centro de Estudios Aplicados en Química laboratory in Quito, Ecuador, to determine the accuracy and performance efficiency of the mineralization process for the determination of total mercury in fish tissue by cold vapor atomic fluorescence spectrophotometry. The use of MARSEasyPrep high-pressure vessels, low amounts of reagents (1 cm3 HNO3, 1 cm3 H2O2, and 1 cm3 HClO4), an irradiation temperature of 210 °C, and 35 min of mineralization time resulted in accurate performance, with recoveries of certified reference material DORM-4 between 90.1% and 105.8%. This is better than the Association of Official Analytical Chemists 2015.01 method, which has a reported accuracy of 81%. The repeatability precision and intermediate precision were established at three concentration levels (0.167, 0.500, and 0.833 mg·kg−1) and expressed as the percentage of the relative standard deviation ranging from 1.5% to 3.0% and 1.7% to 4.2%, respectively. Further, the method was satisfactorily applied to analyze fortified samples of tilapia (Oreochromis niloticus), with recoveries ranging from 98.3% to 104.3%. The instrumental limits of detection and quantification were 0.118 µg·dm−3 and 0.394 µg·dm−3, respectively.

Total mercury and methylmercury in the soil and vegetation of a riparian zone along a mercury-impacted reservoir

The Baihua Reservoir (Guizhou Province, Southwest China) has a history of mercury contamination associated with past acetic acid production activities at the Guizhou Organic Chemical Plant (GOCP). Soil and plant samples collected from riparian zones were analyzed for total Hg (THg) and methylmercury (MeHg) using cold vapor atomic fluorescence spectroscopy. The concentrations of THg and MeHg in soil samples were in the range of 109–371 ng g−1 and 0.32–1.80 ng g−1, respectively. Soils in the riparian zones close to the pollution source (the GOCP) presented higher Hg contamination, with relatively light Hg contamination in remote areas. This suggests a decreasing trend of THg concentrations along the riparian zones, with higher concentrations closer to the pollution source. Significant correlations were found between MeHg and soil organic matter (n = 24, p = 0.01). THg concentrations varied 11.3–161 ng g−1 in aboveground areas and 11.3–193 ng g−1 in underground areas. MeHg concentrations ranged from 0.23 to 1.06 ng g−1 in aboveground areas to 0.13–1.51 ng g−1 in the below ground areas. The vegetation studied showed different concentrations of THg and MeHg and can be considered to be impacted by Hg contamination. Different concentrations of total and methyl mercury were found among the different plant species. The high Hg concentrations in soils and vegetation suggests that the ability of Hg to bioaccumulate in riparian plants is affected by plant physiological characteristics and soil mercury concentrations. Although the bioaccumulation factors (BCFs) of the studied plants were low, their transfer factors (TFs) were >1. Our findings suggest that vegetation exhibiting TFs for THg >1 have the potential for phytoextraction in Hg-impacted riparian zones.

Portable smartphone-based device for on-site detection of Hg2+ in water samples

ABSTRACT In this paper, a smartphone-based portable device was designed for on-site and real-time detection of Hg2+ concentration levels in water samples. A rhodaminespirolactam-based derivative3ʹ,6ʹ-bis(diethylamino)-2-((3,4,5-trimethoxybenzylidene)amino)spiro[isoindoline-1,9ʹ-xanthen]-3-one, which had selective response to Hg2+,was used as Off-On fluorescent probe. The enhanced emission was observed by a high-pixel camera integrated on the smartphone. The grey value was analysed by an android/apple application ‘Detection’, and showed good linearly with Hg2+ concentration ranged from 0.01 to 0.1 μg/ml. The limit of detection (LODs) was found at 0.9 μg/l, which was sensitive enough to detect Hg2+ in industrial wastewater and drinking water. The accuracy of the proposed method was validated by reference Hg2+ solution, and the result was in good agreement with the certified value. Compared with cold vapour atomic fluorescence spectrophotometry, atomic absorption spectrophotometry methods and fluorescence method, etc., the developed platform is simpler, cost-less and portable for on-site and real-time application, and can be used for sharing of in-field sensing data from any remote location to the central water quality monitoring station.

Extraction induced by emulsion breaking for As, Se and Hg determination in crude palm oil by vapor generation-AFS

In this work is presented the development of a method for As and Se determination in crude palm oil samples by hydride generation atomic fluorescence spectrometry and Hg by cold vapor atomic fluorescence spectrometry after ultrasound-assisted emulsification and extraction induced by emulsion breaking (EIEB). The optimization of the method was carried out by multivariate designs. The developed method has presented limits of quantification (LOQ) of 0.72, 0.12, and 1.5 μg L−1 for As, Hg, and Se, respectively. The precisions of the proposed method expressed as repeatability were 0.92, 2.2, and 3.7% RSD for 2 µg L−1 (n = 10) of As, Hg and Se, respectively. The developed methodology was applied in palm oil samples collected in the Bahia State. Concentrations (μg L−1) found in the samples were between <LOQ – 1.3 for As and 3.0–15 for Se. For Hg, all analyzed samples were below the limit of quantification.

DETERMINAÇÃO DE MERCÚRIO EM FÍGADO DE TETRÁPODES MARINHOS POR ESPECTROMETRIA DE FLUORESCÊNCIA ATÔMICA ACOPLADA A GERAÇÃO DE VAPOR FRIO (CV-AFS) E ESPECTROMETRIA DE MASSA COM FONTE DE PLASMA INDUTIVAMENTE ACOPLADO (ICP-MS): UMA COMPARAÇÃO SISTEMÁTICA ENTRE AS DUAS TÉCNICAS

DETERMINATION OF MERCURY IN LIVER OF MARINE TETRAPODS BY COLD VAPOR ATOMIC FLUORESCENCE SPECTROMETRY AND INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY IN BIOLOGICAL SAMPLES: A SYSTEMATIC COMPARISON BETWEEN THE TWO TECHNIQUES. This study compares the techniques cold vapour atomic fluorescence spectrometry (CV-AFS) and inductively coupled plasma mass spectrometry (ICP-MS) for the determination of Hg in biological samples (hepatic tissue from marine tetrapods). Acid digestions were performed for the samples and aliquots of them were analysed by ICP-MS and CV-AFS. To minimize the Hg memory effect in its determination by ICP-MS, gold (200 μg L-1 in 5% v v-1 HCl) was added to the sample digests. The detection limits were 0.02 mg kg-1 for ICP-MS and 0.01 mg kg-1 for CV-AFS. Accuracy was assessed by the calculation of the recovery obtained from TORT-3 (lobster hepatopancreas) certified reference material analysis. Accurate results were obtained for both CV-AFS and ICP-MS. The comparison of the results obtained for hepatic tissue with and without lyophilization showed a significant difference among them (at 95% of confidence level), evidencing losses of Hg in the lyophilization process.

Determining Mercury in Sediment Samples by Extraction Using a Novel-Chelating Reagent Dithiothreitol (DTT) Followed by Cold Vapor Atomic Fluorescence Spectrometry (CV-AFS)

A new analytical protocol has been developed for the determination of mercury in surface sediments using dithiothreitol (DTT) as a new chelating reagent for the extraction. This protocol requires a small sample mass (250 mg), 4.0 mL of a 0.1 M (pH = 9.0) aqueous DTT solution, and sonication for 30 min, followed by cold vapor atomic fluorescence spectrometry (CV-AFS). The limits of detection and quantification determined were 6 and 18 ng g−1, respectively. The method was validated using three standard reference materials, SRM NIST 1646a, PACS-2, and MESS-3, with recoveries in the range of 102-124%. The new analytical protocol was successfully applied in riverine surface sediments, revealing concentrations in the range of 220-340 ng g−1. The results obtained by CV-AFS were compared to those obtained by DMA-80 (direct mercury analyzer). The linear regression equation obtained was [CV-AFS] = (0.91 ± 0.07)[DMA-80] + (0.04 ± 0.02), revealing no systematic difference between the analytical methods. Hence, the proposed method does not require the complete digestion of the sediment, and was found to be comprehensive, simple, accurate and suitable to be employed for determination of mercury in sediment samples.

Modification of the EPA method 1631E for the quantification of total mercury in natural waters

To support the effectiveness of the Minamata Convention, the accurate determinations of mercury (Hg) in natural waters is an important but certainly challenging task due to the low concentrations expected in ambient samples. Mercury contamination may occur from many sources such as the unproperly-cleaning of storage bottles or the use of reagents for sample analysis with Hg traces, thus leading the analyst to easily run into errors. In our work, we propose some key modifications to the United States Environmental Protection Agency(EPA) method 1631E aimed at reducing the Hg contamination of reagents, storage containers, and minimizing the carryover effect in the instrumental line of sampling. The changes introduced have been tailored for the use of the method with cold vapor atomic fluorescence spectroscopy (CV-AFS) instrumentation and tested as part of a United Nations Environment Program (UNEP) ring test. Although the edited method was tested with natural water samples, the proposed method improvements can also apply to the Hg analysis in solid matrices that require the prior acid digestion of the samples.•A customized version of the EPA method 1631E is proposed for the analysis of aqueous samples.•New protocols for the reduction of contamination in the storage bottles and reagents used for the preparation of BrCl solution are provided.•A useful strategy for the control of the memory effect is included.