New insights and rethinking of cinnabar for chemical and its pharmacological dynamics.

Cinnabar is an attractive mineral with many different uses. It is reported that cinnabar is one of the traditional Chinese's medicines extensively use. The main objective of this critical review is to identify the current overview, concept and chemistry of cinnabar, which includes the process developments, challenges, and diverse options for pharmacology research. It is used as a medicine through probable toxicity, especially when taking overdoes. This review is the first to describe the toxicological effects of cinnabar and its associated compounds. Nuclear magnetic resonance (NMR) dependent metabolomics could be useful for examination of the pharmaceutical consequence. The analysis indicated that the accurate preparation methods, appropriate doses, disease status, ages with drug combinations are significant factors for impacting the cinnabar toxicity. Toxicologically, synthetic mercury sulfide or cinnabar should be notable for mercuric chloride, mercury vapor and methyl mercury for future protection and need several prominent advancements in cinnabar research.

A sulfur-resistant CuS-modified active coke for mercury removal from municipal solid waste incineration flue gas.

Adsorption is a typical method for air pollutant removal from flue gas. A CuS-modified active coke (CuS/AC) sorbent was developed to improve the elemental mercury removal efficiency from municipal solid waste incineration (MSWI) flue gas. The influences of the loading amount of CuS, reaction temperature, and flue gas components including O2, SO2, H2O, and HCl on Hg0 removal efficiency were investigated, respectively. The results showed that the mercury adsorption capacity of CuS/AC(20%) sorbent was about 7.17 mg/g with 50% breakthrough threshold, which is much higher than that of virgin active coke. The analysis of XPS indicated that HgS was the main species of mercury on spent CuS/AC, which implied that adsorption and oxidation were both included in Hg0 removal. S22- played a vital role in the oxidation of physically adsorbed Hg0. Meanwhile, the common components of MSWI flue gas exhibited no significant inhibition effect on Hg0 removal by CuS/AC sorbent. CuS/AC sorbent is a promising sorbent for the mercury removal from MSWI flue gas.

Interfacing nanoliter liquid chromatography and inductively coupled plasma mass spectrometry with an in-column high-pressure nebulizer for mercury speciation.

Metal speciation analysis of microsamples in the clinical, biological and forensic fields is important for elucidating the metals' toxicity, mobility and metabolic behaviors of metals. Such analysis may be achieved by nanoliter high-performance liquid chromatography (nanoHPLC) hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). In this work, an in-column high-pressure nebulizer (ICHPN) was developed to enhance the sensitivity and the separation efficiency of the sheathless nanoHPLC-ICP-MS coupling. The ICHPN consists of two concentric fused-silica capillaries with tapered tips connected via a PEEK tee, where C18 silica particles with a size of 5 µm were packed in the tapered inner capillary based on the keystone effect. Combining a heated single pass spray chamber with a makeup gas, the ICHPN was capable of independently optimizing the nebulization efficiency and the transport efficiency. The ICHPN offered high sensitivities, low detection limits and good precision at nanoflow rates. Compared with commercial nebulizers, the ICHPN fabrication was simple, rapid, reproducible and inexpensive. By implementing the ICHPN, we achieved rapid separation of four mercury species, i.e., Hg2+ and methyl-, ethyl- and phenylmercuric chloride, within 8.0 min with good resolution (2.0-13.9). Detection limits of 0.044-0.13 µg L-1 were obtained with precisions of peak heights and areas ranging from 1.5 to 3.5% for a 50 µg L-1 standard solution. Good agreement between the determined and certified values of mercury species in a certified reference material of caprine blood (SRM 955c) together with good recoveries (93-101%) validated the accuracy of the method.

Hg Compound-Specific Isotope Analysis at Ultratrace Levels Using an on Line Gas Chromatographic Preconcentration and Separation Strategy Coupled to Multicollector-Inductively Coupled Plasma Mass Spectrometry.

Stable Hg isotope analyses are nowadays widely employed to discriminate Hg sources and understand its biogeochemical cycle. Until now, total Hg isotopic compositions have been mainly used but Hg compound-specific isotopic analysis (CSIA) methodologies are emerging. Online Hg-CSIA were limited to samples containing high concentrations, but in this work we overcome this limitation for the measurement of inorganic (IHg) and monomethylmercury (MMHg) by gas chromatography hyphenated to multicollector-inductively coupled plasma mass spectrometry (GC/MC-ICPMS) through the use of an automated online preconcentration strategy, allowing injection volumes up to 100 times larger than usual. The preconcentration of Hg species and subsequent transfer to the column were achieved by a programmed temperature vaporization (PTV) injector fitted with a packed liner. The PTV parameters were first optimized using a quadrupole ICPMS, and then its suitability for Hg-CSIA was evaluated with long-term replicate analysis of various standards and reference materials (RMs). The large preconcentration capability enables analyses with Hg concentrations in the organic solvent 2 orders of magnitude lower than the previous conventional GC/MC-ICPMS method, but a compound specific standard bracketing procedure was required for MMHg in order to correct for the differential behavior of Hg species in the liner. The external reproducibility of the method ranged from 0.19 to 0.39 ‰ for Δ199Hg and δ202Hg (as 2 SD, n = 143-167) depending on the species. The analysis of various RMs demonstrated the applicability to environmental samples with species concentrations down to about 150 ng g-1. This new methodology opens the way for a much wider range of online Hg-CSIA measurements that will improve our understanding of the Hg biogeochemical cycle.

A review of cinnabar (HgS) and/or realgar (As4S4)-containing traditional medicines.

ETHNOPHARMOCOLOGICAL RELEVANCE: Herbo-metallic preparations have a long history in the treatment of diseases, and are still used today for refractory diseases, as adjuncts to standard therapy, or for economic reasons in developing countries. AIM OF THE REVIEW: This review uses cinnabar (HgS) and realgar (As4S4) as mineral examples to discuss their occurrence, therapeutic use, pharmacology, toxicity in traditional medicine mixtures, and research perspectives. MATERIALS AND METHODS: A literature search on cinnabar and realgar from PubMed, Chinese pharmacopeia, Google and other sources was carried out. Traditional medicines containing both cinnabar and realgar (An-Gong-Niu-Huang Wan, Hua-Feng-Dan); mainly cinnabar (Zhu-Sha-An-Shen Wan; Zuotai and Dangzuo), and mainly realgar (Huang-Dai Pian; Liu-Shen Wan; Niu-Huang-Jie-Du) are discussed. RESULTS: Both cinnabar and realgar used in traditional medicines are subjected to special preparation procedures to remove impurities. Metals in these traditional medicines are in the sulfide forms which are different from environmental mercurials (HgCl2, MeHg) or arsenicals (NaAsO2, NaH2AsO4). Cinnabar and/or realgar are seldom used alone, but rather as mixtures with herbs and/or animal products in traditional medicines. Advanced technologies are now used to characterize these preparations. The bioaccessibility, absorption, distribution, metabolism and elimination of these herbo-metallic preparations are different from environmental metals. The rationale of including metals in traditional remedies and their interactions with drugs need to be justified. At higher therapeutic doses, balance of the benefits and risks is critical. Surveillance of patients using these herbo-metallic preparations is desired. CONCLUSION: Chemical forms of mercury and arsenic are a major determinant of their disposition, efficacy and toxicity, and the use of total Hg and As alone for risk assessment of metals in traditional medicines is insufficient.

Evaluation of the potential nephrotoxicity and mechanism in rats after long-term exposure to the traditional Tibetan medicine tsothel.

CONTEXT: Tsothel, a traditional Tibetan medicine, is regarded as 'the king of essences'. Nevertheless, tsothel has aroused serious concern regarding its biosafety because its main component is HgS. Unfortunately, toxicological studies on tsothel are scarce. OBJECTIVE: As inorganic mercury has high affinity for the kidney, the present investigation was designed to determine the potential nephrotoxicity and mechanism of tsothel. MATERIALS AND METHODS: Sprague-Dawley rats were orally administered different doses of tsothel (0, 66.70, 33.35 and 16.68 mg/kg) daily for 180 days, followed by the withdrawal of tsothel for 120 days. Then, the related nephrotoxicity was examined by the ICP-MS, ELISA, colorimetric, RT-PCR, HE staining, immunohistochemical staining and flow cytometry methods. RESULTS: Although tsothel administration led to a large accumulation of Hg (794.25 ± 464.30 ng/g in the 66.70 mg/kg group, 775.75 ± 307.89 ng/g in the 33.35 mg/kg group and 532.60 ± 356.77 ng/g in the 16.68 mg/kg group) in the kidney after 120 days of tsothel withdrawal, the blood CREA and BUN, urinary Kim-1, NAG, RBP and ß2-MG, renal SOD, MDA, pathology, proliferation, apoptosis and cell cycle had no significant changes compared with the control group. Additionally, the high GSH content (318.87 ± 44.19 nmol/mL in the 33.35 mg/kg group) and the relative expression levels of Kim-1 (1.08 ± 0.11 in the 33.35 mg/kg group), MT-1 (1.46 ± 0.10 in the 66.70 mg/kg group, 1.61 ± 0.19 in the 33.35 mg/kg group and 1.57 ± 0.14 in the 16.68 mg/kg group) and GST-Pi (1.76 ± 0.89 in the 33.35 mg/kg group) mRNA recovered to normal after tsothel withdrawal. Interestingly, the change trend of GST-Pi gene expression was consistent with the change trend of GSH activity. CONCLUSIONS: Overall, our study shows that tsothel administration did not induce overt nephrotoxicity but did have reversible stress-related effects. These results suggest that tsothel affects stress response mechanisms with the involvement of detoxifying enzyme systems. The formulation method and chemotype could play a role in the reduced toxicity potential of tsothel compared to common mercurials.

Ion-pairing reversed-phase chromatography coupled to inductively coupled plasma mass spectrometry as a tool to determine mercurial species in freshwater fish.

Most of analytical community is focused on reversed phase high performance liquid chromatography (RP-HPLC) for mercury speciation by employing mobile phases comprising of high salts and moderate amounts of organic solvents. This study aims at rapid mercury speciation analysis by ion-pairing RP-HPLC with inductively coupled plasma mass spectrometry (ICP-MS) detection only using low salts for the sake of green analytical chemistry. Two ion-pairing HPLC methods were developed on individual usage of positively and negatively charged ion-pairing reagents (tetrabutylammonium hydroxide -TBAH and sodium dodecylbenzene sulfonate -SDBS), where sodium 3-mercapto-1-propysulfonate (MPS) and l-cysteine (Cys) were individually added in mobile phases to transform mercury species into negative and positive Hg-complexes for good resolution. Addition of phenylalanine was also utilized for rapid baseline separation in combination of short C18 guard columns. Optimum mobile phases of 2.0mM SDBS+2.0mM Cys+1.0mM Phe (pH 3.0) and 4.0mM TBAH+2.0mM MPS+2.0mM Phe (pH 6.0) both achieved baseline separation of inorganic mercury (Hg2+), methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) on two consecutive 12.5-mm C18 columns. The former mobile phase was selected for mercury speciation in freshwater fish because of short separation time (3.0min). Detection limits of 0.015 for Hg2+, 0.014 for MeHg, 0.028 for EtHg and 0.042µgL-1 for PhHg were obtained along with satisfactory precisions of peak height and area (1.0-2.8% for 5.0µgL-1 Hg-mixture standard). Good accordance of determined values of MeHg and total mercury in certified reference materials of fish tissue (GBW 10029) and tuna fish (BCR-463) with certified values as well as good recoveries (91-106%) proved good accuracy of the proposed method. An example application to freshwater fish indicated its potential in routine analysis, where MeHg was presented at 3.7-20.3µgkg-1 as the dominate species.

A New Strategy to Refine Crude Indian Sardine Oil.

Current work aims to develop a refining process for removing phospholipids, free fatty acids (FFA), and metal ions without affecting n-3 polyunsaturated fatty acid (n-3 PUFA) esters present in the crude Indian sardine oil. Sardine oil was subjected to degumming with various acids (orthophosphoric acid, acetic acid, and lactic acid), conventional and membrane assisted deacidification using various solvents (methanol, ethanol, propanol and butanol) and bleaching with bleaching agents (GAC, activated earth and bentonite) and all the process parameters were further optimized. Degumming with 5%(w/w) ortho phosphoric acid, two stage solvent extraction with methanol at 1:1 (w/w) in each stage and bleaching with 3% (w/w) activated charcoal loading, at 80ºC for 10 minutes resulted in the reduction of phospholipid content to 5.66 ppm from 612.66 ppm, FFA to 0.56% from 5.64% with the complete removal of iron and mercury. Under these conditions, the obtained bleached oil showed an enhancement of n-3 PUFA from 16.39 % (11.19 Eicosapentaenoic acid (EPA) + 5.20 Docosahexaenoic acid (DHA)) to 17.91 % (11.81 EPA + 6.1 DHA). Replacing conventional solvent extraction with membrane deacidification using microporous, hydrophobic polytetrafluoroethylene membrane (PTFE), resulted in a lesser solvent residue (0.25% (w/w)) in the deacidified oil. In view of lack of reports on refining of n-3 PUFA rich marine oils without concomitant loss of n-3 PUFA, this report is significant.

Removal and speciation of mercury compounds in flue gas from a waste incinerator.

The management and control of mercury emissions from waste incinerators have become more significant, because waste incinerators are sinks to treat mercury-containing consumer products. This study investigated the effects of mercury concentrations and waste incineration temperatures on mercury speciation using a lab-scale experimental instrument. The removal characteristics of different mercury species were also investigated using an apparatus to simulate the fabric filter with a thin layer of additives such as Ca(OH)2 and NaHCO3, activated carbon (AC), and fly ash. HgCl2 generation rates peaked at 800°C for initial Hg(0) concentrations of 0.08-3.61 mg/Nm(3) in the presence of 400 ppm HCl. A linear relationship was established between the generation rate of HgCl2 and the logarithmic value of initial mercury concentration. Fly ash proved highly efficient in mercury removal, being equal or superior to AC. On the other hand, Ca(OH)2 and NaHCO3 were shown to have no effects on mercury removal. In the dry-scrubbing process, alkali agent is often sprayed in amounts beyond those stoichiometrically required to aid acidic gas removal. The research suggests, however, that this may hinder mercury removal from the flue gas of solid waste incinerators.

Mercury isotope signatures in contaminated sediments as a tracer for local industrial pollution sources.

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) may cause characteristic isotope signatures of different mercury (Hg) sources and help understand transformation processes at contaminated sites. Here, we present Hg isotope data of sediments collected near industrial pollution sources in Sweden contaminated with elemental liquid Hg (mainly chlor-alkali industry) or phenyl-Hg (paper industry). The sediments exhibited a wide range of total Hg concentrations from 0.86 to 99 µg g(-1), consisting dominantly of organically-bound Hg and smaller amounts of sulfide-bound Hg. The three phenyl-Hg sites showed very similar Hg isotope signatures (MDF δ(202)Hg: -0.2‰ to -0.5‰; MIF Δ(199)Hg: -0.05‰ to -0.10‰). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (δ(202)Hg: -2.1‰ to 0.6‰; Δ(199)Hg: -0.19‰ to 0.03‰) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1‰ heavier in δ(202)Hg than organically-bound Hg. The selectivity of the sequential extraction was tested on standard materials prepared with enriched Hg isotopes, which also allowed assessing isotope exchange between different Hg pools. Our results demonstrate that different industrial pollution sources can be distinguished on the basis of Hg isotope signatures, which may additionally record fractionation processes between different Hg pools in the sediments.

A new guar gum-based adsorbent for the removal of Hg(II) from its aqueous solutions.

Modification of biopolymers by oxidation is an easy process to develop effective adsorbents for the removal of toxic metal ions from their aqueous solutions. In the present study, guar gum (GG) was crosslinked with epichlorohydrin and then oxidized to the polydialdehyde form (GG-clPDA). The latter was converted to a Schiff-base, GG-clCHN(CH2)6NCHGG, by reaction with hexamethylenediamine. Different forms of the modified GG were characterized by SEM, FTIR and XRD and investigated as adsorbents for the removal of Hg(II) ions from their aqueous solutions. The adsorption process was carried out through the variation of time, temperature, pH and initial concentration of Hg(II) ions. GG-clCHN(CH2)6NCHGG was observed to be an efficient adsorbent with a maximum adsorption capacity of 41.13 mg/g. It is reusable up to five cycles at the optimum conditions obtained for the maximum ions uptake. The kinetic data generated fit the Freundlich isotherm and pseudo-second order kinetics.

Assessment of dispersive liquid-liquid microextraction for the simultaneous extraction, preconcentration, and derivatization of Hg2+ and CH3Hg+ for further determination by GC-MS.

This work reports the development of a dispersive liquid-liquid microextraction method for the simultaneous extraction, preconcentration, and derivatization of Hg(2+) and CH3Hg(+) species from water samples for further determination by GC-MS. Some parameters of the proposed method, such as volume and type of disperser and extraction solvent, and Na[B(C6H5)4] concentration were investigated using response surface methodology. Suitable recoveries were obtained using 80 µL C2 Cl4 (as extraction solvent), 1000 µL ethanol (as disperser solvent), and 300 µL 2.1 mmol/L Na[B(C6H5)4] (as derivatizing agent). Accuracy was evaluated in terms of recovery and ranged from 87 to 99% with RSD values <7%. In addition, a certified reference material of water (NIST 1641d) was analyzed and agreed with the certified value about 107% (for Hg(2+)), with RSD values <8.5%. LODs were 0.3 and 0.2 µg/L, with enrichment factors of 112 and 115 for Hg(2+) and CH3Hg(+), respectively. The optimized method was applied for the determination of Hg(2+) and CH3Hg(+) in tap, well, and lake water samples.

Ionic liquids dispersive liquid-liquid microextraction and HPLC-atomic fluorescence spectrometric determination of mercury species in environmental waters.

An ionic liquid (IL) based dispersive liquid-liquid microextraction combined with HPLC hydride generation atomic fluorescence spectrometry method for the preconcentration and determination of mercury species in environmental water samples is described. Four mercury species (MeHg(+), EtHg(+), PhHg(+), and Hg(2+)) were complexed with dithionate and the neutral chelates were extracted into IL drops using dispersive liquid-liquid microextraction. Variables affecting the formation and extraction of mercury dithizonates were optimized. The optimum conditions found were as follows: IL-type and amount, 0.05 g of 1-octyl-3-methylimidazolium hexafluorophosphate; dispersive solvents type and amount, 500 µL of acetone; pH, 6; extraction time, 2 min; centrifugation time, 12 min; and no sodium chloride addition. Under the optimized conditions, the detection limits of the analytes were 0.031 µg/L for Hg(2+), 0.016 µg/L for MeHg(+), 0.024 µg/L for EtHg(+), and 0.092 µg/L for PhHg(+), respectively. The repeatability of the method, expressed as RSD, was between 1.4 and 5.2% (n = 10), and the average recoveries for spiked test were 96.9% for Hg(2+), 90.9% for MeHg(+), 90.5% for EtHg(+), 92.3% for PhHg(+), respectively. The developed method was successfully applied for the speciation of mercury in environmental water samples.

Investigation of adsorption behavior of mercury on Au(111) from first principles.

The structural and electronic properties of Hg, SO(2), HgS, and HgO adsorption on Au(111) surfaces have been determined using density functional theory with the generalized gradient approximation. The adsorption strength of Hg on Au(111) increases by a factor of 1.3 (from -9.7 to -12.6 kcal/mol) when the number of surface vacancies increases from 0 to 3; however, the adsorption energy decreases with more than three vacancies. In the case of SO(2) adsorption on Au(111), the Au surface atoms are better able to stabilize the SO(2) molecule when they are highly undercoordinated. The SO(2) adsorption stability is enhanced from -0.8 to -9.3 kcal/mol by increasing the number of vacancies from 0 to 14, with the lowest adsorption energy of -10.2 kcal/mol at 8 Au vacancies. Atomic sulfur and oxygen precovered-Au(111) surfaces lower the Hg stability when Hg adsorbs on the top of S and O atoms. However, a cooperative effect between adjacent Hg atoms is observed as the number of S and Hg atoms increases on the perfect Au(111) surface, resulting in an increase in the magnitude of Hg adsorption. Details of the electronic structure properties of the Hg-Au systems are also discussed.

In vitro studies on dissolved substance of cinnabar: chemical species and biological properties.

UNLABELLED: Cinnabar is one of traditional Chinese medicines widely used in many Asian countries. It is also a medicine with potential toxicity especially when taking overdose. Up to date, studies on the mechanism of the biological activity of cinnabar were still insufficient. AIM OF THE STUDY: To investigate the possible bioactive species from cinnabar after oral administration, which is the fundamental of biological effects of cinnabar. MATERIALS AND METHODS: Under mimetic intestinal and gastric conditions, the chemical components dissolved from cinnabar were analyzed by infrared spectroscopy (IR) and Raman spectroscopy. Furthermore, binding of mercuric species of cinnabar extractions to human serum protein (HSA) was characterized and their intestinal permeability was determined using the Caco-2 cell monolayer. The cytotoxicity of cinnabar extractions was assessed on human kidney-2 (HK-2) cell. RESULTS: Major dissolved species included mercuric polysulfide (i.e. HgS(2)(OH)(-) and Hg(3)S(2)Cl(2)). The apparent permeability coefficient (P(app)) of mercuric polysulfides was (1.6+/-0.3)x10(-6)cm/s, which is slightly lower than that of mercuric chloride (HgCl(2)). Unlike HgCl(2), mercuric polysulfides exhibited two tightly binding sites to HSA and had little effect on viability of HK-2 cells. CONCLUSION: Mercuric polysulfides, as the major dissolved components, may serve as the active species of cinnabar exhibiting pharmacological and/or toxicological effects.

Immobilization of methylene blue onto bentonite and its application in the extraction of mercury (II).

Methylene blue was immobilized onto bentonite (BNT). The modified clay (MB-BNT) was used to extract Hg(2+) at pH 6.0 yielding Hg-MB-BNT. BNT, MB-BNT and Hg-MB-BNT were characterized by X-ray diffractometry, infrared spectra, and elemental and thermogravimetric analyses. MB is suggested to be intercalated into the major phase of BNT; montmorillonite mineral (MMT), lying parallel to the aluminosilicate layers, with a capacity of 36 mequiv./100g. MB-BNT shows good stability in 0.1-1M hydrochloric or nitric acids, ammonium hydroxide, and concentrated Na(+), K(+) or NH(4)(+) chlorides or iodides. It shows good selectivity towards Hg(2+) with an extraction capacity of 37 mequiv./100g in the presence of I(-) giving rise to a ratio of MB/Hg(2+)/I(-) 1:1:3 in the clay phase. Extracted Hg(2+) could be quantitatively recovered by ammonia buffer at pH 8.5. MB-BNT was successfully applied to recover Hg(2+) from spiked natural water and cinnabar mineral samples using the optimum conditions; pH 6.0, time of stirring 10 min and 10 mL of 0.05 M NH(4)Cl/NH(4)OH at pH 8.5 as eluent.

Determination of organic and inorganic mercury species in water and sediment samples by HPLC on-line coupled with ICP-MS.

This paper describes a preconcentration method for Hg(2+) and MeHg(+) in water samples using sodium diethyldithiocarbamate immobilized in polyurethane foam (PU-NaDDC) and an extraction method for several mercury species in sediment samples, including MeHg(+), EtHg(+) and PhHg(+), which is simple, rapid, and uses a single organic solvent. Separation and measurement were done by high-performance liquid chromatography on-line with inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Initially, the test of recovery was applied using procedures compatible with HPLC. Under the optimum extraction conditions, recoveries of 96.7, 96.3 and 97.3% were obtained for MeHg(+), EtHg(+), and PhHg(+), respectively, from n=4 spiked sediment samples. This study also demonstrates that the combination of solid-phase extraction on PU-NaDDC with HPLC separation and ICP-MS detection is an effective preconcentration procedure for simultaneous measurement of Hg(2+) and MeHg(+) at ultra-trace levels in water samples. The application of the proposed procedure to the determination of mercury species in drinking water sample was investigated. The proposed method clearly gave satisfactory average recoveries between 93.7 and 101.5%.

Speciation analysis of mercury in cereals by liquid chromatography chemical vapor generation inductively coupled plasma-mass spectrometry.

A simple and rapid procedure for the separation and determination of inorganic, methyl, and ethyl mercury compounds was described using liquid chromatography (LC) followed by vapor generation inductively coupled plasma-mass spectrometry (VG-ICP-MS). Well resolved chromatograms were obtained within 5 min by reversed-phase liquid chromatography with a C8 column as the stationary phase and a pH 4.7 solution containing 0.5% v/v 2-mercaptoethanol and 5% v/v methanol as the mobile phase. The separated mercury compounds were converted to mercury vapors by an in situ nebulizer/vapor generation system for their introduction into ICP. The concentrations of NaBH4 and HNO3 required for vapor generation were also optimized. The method was applied for the speciation of mercury in reference materials NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour and also rice flour and wheat flour samples purchased locally. The accuracy of the procedure was verified by analyzing the certified reference material NRCC DOLT-3 Dogfish Liver for methyl mercury. Precision between sample replicates was better than 13% for all the determinations. The detection limits of the mercury compounds studied were in the range 0.003-0.006 ng Hg mL(-1) in the injected solutions, which correspond to 0.02-0.06 ng g(-1) in original flour samples. A microwave-assisted extraction procedure was adopted for the extraction of mercury compounds from rice flour, wheat flour, and fish samples using a mobile phase solution.

Preparation of xylenol orange functionalized silica gel as a selective solid phase extractor and its application for preconcentration--separation of mercury from waters.

A new selective solid phase extractor was prepared from silica gel modified with xylenol orange (SGMXO). The solid phase extractor is stable in 6molL(-1) HCl, common organic solvents, and pH 1.0-9.0 buffer solutions. In the batch experiments, Hg(II) can be adsorbed on SGMXO at pH 1.0 with 90.0% retention, whereas the retention of other common coexisting metal ions such as Cd(II), Pb(II), Cu(II), Ni(II), Co(II), Mn(II), Zn(II), and Fe(III) is less than 4.1%.. The adsorption equilibration for Hg(II) was achieved within 3min. At optimum conditions, the adsorption capacity of the extractor is 18.26micromolg(-1) of dry modified silica gel, and the preconcentration factor is as high as 333. The recovery is still higher than 95% for the preconcentration of 10ngmL(-1) Hg(II). The new solid phase extractor has been used for the preconcentration of low level of Hg(II) in surface water, tap water in chemistry laboratory and student's dormitory and a simulated sea water samples, recoveries of 98.2-100.6% were obtained. It is showed that low level of Hg(II) can be effectively preconcentrated by this new selective solid phase extractor.

Removal of inorganic mercury from aqueous solutions by biomass of the marine macroalga Cystoseira baccata.

The ability of Cystoseira baccata algal biomass to remove Hg(II) from aqueous solutions is investigated. The mercury biosorption process is studied through batch experiments at 25 degrees C with regard to the influence of contact time, initial mercury concentration, solution pH, salinity and presence of several divalent cations. The acid-base properties of the alga are also studied, since they are related to the affinity for heavy metals. The studies of the pH effect on the metal uptake evidence a sharp increasing sorption up to a pH value around 7.0, which can be ascribed to changes both in the inorganic Hg(II) speciation and in the dissociation state of the acid algal sites. The sorption isotherms at constant pH show uptake values as high as 178 mg g(-1) (at pH 4.5) and 329 mg g(-1) (at pH 6.0). The studies of the salinity influence on the Hg(II) sorption capacity of the alga exhibit two opposite effects depending on the electrolyte added; an increase in concentration of nitrate salts (NaNO3, KNO3) slightly enhances the metal uptake, on the contrary, the addition of NaCl salt leads to a drop in the sorption. The addition of different divalent cations to the mercury solution, namely Ca2+, Mg2+, Zn2+, Cd2+, Pb2+ and Cu2+, reveals that their effect on the uptake process is negligible. Finally, the equilibrium sorption results are compared with predictions obtained from the application of a simple competitive chemical model, which involves a discrete proton binding constant and three additional constants for the binding of the main neutral inorganic Hg(II) complexes, Hg(Cl)2, HgOHCl and Hg(OH)2, to the algal surface sites.