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1.
Analytical aspects of the determination of inorganic mercury (Hg) species by thermal desorption followed by atomic absorption spectrometry (AAS) detection were investigated in this work. Characteristic Hg release curves of the following species were observed: Hg0, HgCl2, HgO, HgSO4, HgS, and the Hg bound to humic acids. Particular attention was dedicated to the thermal stability and change of bond of Hg0 in the following matrices: sand, kaolinite, granite, peat, power plant ash, and soil. The bond of elemental Hg in environmental materials was described on basis of this experiment. Contaminated soil samples from two locations in the Czech Republic were investigated by thermal desorption analysis. Afterwards, the contents of volatile and plant-available Hg in the studied samples were determined. The determination of Hg0 using the thermal method was related to the results of liquid sequential extraction. The development of Hg speciation and the stability of Hg were assessed on basis of the data obtained. Thus, the analytical procedure used is a suitable tool for the study of inorganic Hg species in contaminated soils.  相似文献   

2.
Mercury forms in contaminated environmental samples were studied by means of sequential extraction and thermal desorption from the solid phase. The sequential extraction procedure involved the following fractions: water soluble mercury, mercury extracted in acidic conditions, mercury bound to humic substances, elemental Hg and mercury bound to complexes, HgS, and residual mercury. In addition to sequential extraction, the distribution of mercury species as a function of soil particles size was studied. The thermal desorption method is based on the thermal decomposition or desorption of Hg compounds at different temperatures. The following four species were observed: Hg0, HgCl2, HgS and Hg(II) bound to humic acids. The Hg release curves from artificial soils and real samples were obtained and their applicability to the speciation analysis was considered.   相似文献   

3.
Here we present a new method for sequential selective extractions (SSEs) for Hg in geological solids, validated with extensive quality assurance procedures. Mercury was separated into fractions which “make sense” biogeochemically, rather than being identified by specific compounds. Experiments elucidated the effects of extraction time, solids-to-liquid ratio, and alternate solvents in natural samples, reference materials, and pure compounds. Compounds tested included HgS (red and black), HgCl2, Hg0, Hg2Cl2, HgSe, HgO, Hg(II) adsorbed on goethite, Hg-humate, and gold amalgamated Hg. Based on these findings, a five-step sequence of extractions was established to separate the compounds into biogeochemically distinct categories. The fractions and leaching media were as follows: F1 (deionized water), F2 (0.01 M HCl+0.1 M CH3COOH), F3 (1 M KOH), F4 (12 M HNO3), and F5 (aqua regia). Method blanks and method detection limits (MDLs) of 0.1-5 ng/g were obtained for the various analytical fractions, depending on the reagent concentrations used. Precision ranged from 2 to 8% for the major fractions in a sample, but increased to 2-40% for fractions making up <5% of the total. Recovery of total Hg by the sum of species in reference materials showed that the accuracy of the method ranges from 90 to 105%. Methylation potential, determined by anoxic incubation sample aliquots with biologically active sediments, showed that inorganic Hg extracted in the F3 fraction is most strongly correlated with methylation potential. In most natural and sediment incubation samples, the majority of Hg present was found either in the F3 or F5 fractions.  相似文献   

4.
In this study, a diffusion-type device for generating gaseous mercuric chloride (HgCl2) was systematically evaluated and applied to validate the annular denuder method for sampling gaseous HgCl2 species in a synthetic gas stream. The results show that it takes at least 48 h for the system to reach a steady-state condition after the diffusion cell reaches the temperature set-point and the carrier gas is activated. The primary Hg species from the source was proven to be HgCl2. In the temperature range from –5.00 to 11.80 °C, the Hg emission rates from the source vary from 1.8 to 14.2 pg min–1. It is shown that, under the experimental conditions examined, KCl-coated annular quartz denuders designed for ambient reactive gaseous mercury (RGM) collection could quantitatively collect HgCl2. It is also demonstrated that the impactors used to remove coarse airborne particulate matter could lead to a loss of up to one third of the HgCl2 in the gas stream.  相似文献   

5.
The syntheses of [Hg(X)OAc] (OAc=acetate; X=CN, Cl, Br, I, SCN) are reported, and the crystal structure of the cyano complex has been determined. The asymmetric unit contains two [Hg(CN)OAc] molecules which show almost linear C–Hg–O bonding (Hg–C=2.019(13), 2.016(11) Å; Hg–O=2.067(9), 2.058(8) Å; C–Hg–O=176.0(4), 172.3(5)°), with only one of the two acetate oxygen atoms bound directly to the mercury atom. Secondary HgO and HgN contacts in the range 2.6–2.8 Å are about 0.2 Å shorter than the secondary HgO contacts in the corresponding X=Ph complex. The ν(HgX) and ν(HgO) modes have been assigned in the IR and Raman spectra of [Hg(X)OAc] (X=CN, Cl, Br, I, SCN); these spectra show that the complexes have structures with essentially linear O–Hg–X bonding, similar to that of the cyanide. Solid-state 199Hg MAS NMR spectra have been recorded for HgX2 (X=CN, Cl) and [Hg(X)OAc] (X=Me, Ph, CN, Cl, SCN), and spinning sideband analysis has been used to determine the 199Hg shielding anisotropy and asymmetry parameters Δσ and η. A semi-empirical method for the calculation of the local paramagnetic contribution to the shielding is given, and a linear relationship between Δσ and the isotropic shielding σiso which is predicted by this model for linear HgXY species is found to be obeyed reasonably well by the experimental data for HgX2 and [Hg(X)OAc]. The same method is used to analyse the effects of secondary bonding on the 199Hg shielding parameters. The 13C MAS NMR spectrum of [Hg(SCN)OAc] shows 2J(199Hg13C) and 3J(199Hg13C) coupling to the acetate carbon atoms, with magnitudes similar to those found previously for Hg(OAc)2. The CN carbon signals in Hg(CN)2 and [Hg(CN)OAc] are split into 2:1 doublets due to residual dipolar coupling to the quadrupolar 14N nucleus.  相似文献   

6.
The crystal structures have been determined of CH3NH3HgCl3, (CH3NH3)2HgCl4, and CH3NH3Hg2Cl5. In (CH3NH3)2HgCl4 the HgII atom is tetrahedrally coordinated by four Cl atoms with Hg? Cl bond lengths of 2.464 to 2.478 Å. In the other two compounds the HgII atom is involved in two short covalent Hg? Cl bonds, forming a pseudo HgCl2 molecule and two much longer bridging Hg? Cl bonds. The methylammonium groups are connected by hydrogen bonds to the chlorine atoms. The nature of the hydrogen bonding scheme probably causes disorder of the methylammonium groups.  相似文献   

7.
The products of the radiation-chemical and thermal decomposition of mercury fulminate were examined by IR spectroscopy and X-ray diffraction analysis. Upon radiolysis to 20% conversion, the fulminate ion underwent decomposition (G (decomposition) = 20 molecule/100 eV) with the formation of HgO (G = 9 ± 1 molecule/100 eV), CN ions, and CO2. The final solid products of the radiolysis are Hg(CNH)2, a cyanide complex, the mercury carbonate oxide HgCO3 · 3HgO, the mercury cyanide oxide Hg(CN)2 · HgO, and paracyanogen (CN)n. In the thermolysis, the final solid products of decomposition are the mercury carbonate oxide HgCO3 · 2HgO, a cyanide complex, and the cluster HgnCmNoOp.  相似文献   

8.
A simple and rapid microwave-assisted extraction (MAE) technique has been developed for the determination of water-soluble inorganic species (cations: Na+, NH4+, K+, Ca2+ and Mg2+ and anions: F, Cl, NO3, PO43– and SO42–) in airborne particulate matter. The analytes were extracted under different treatment conditions such as microwave power and extraction time. They were quantified using ion chromatography. The observed concentrations and recovery yields obtained under different conditions were compared. The results of a comparison between this MAE and sonication using NIST SRM 1648 are also given in this paper. The optimized MAE technique gave results in good agreement with the values obtained by the sonication. For some ions, for example Mg2+ and K+, recovery was low with both techniques. The results demonstrated that the optimized MAE is fast and efficient compared with conventional ultrasonic extraction. Urban airborne particles were collected and subjected to the MAE followed by the IC analysis to determine the relative proportions of different water-soluble inorganic species. These results are briefly discussed.  相似文献   

9.
Transport of mercury species in aquatic media is strongly affected by sorption processes on both organic and inorganic particles, and such mass transfer reactions are governed by speciation of this contaminant in the environment. The present research investigates the uptake of inorganic HgII species by sorbent materials based on polysiloxane-immobilized amine or thiol ligands, with the goal to highlight the effect of speciation on the sorption processes. Mercury binding was studied as a function of pH and chloride concentration to cover a wide range of species, including some among the most widely encountered forms in natural medium (HgCl42−, HgCl3, HgCl2, Hg(OH)2). It was found on the one hand that all these species are liable to be removed from solution by strong binding to silica gels grafted with mercaptopropyl groups. On the other hand, the use of silica bearing aminopropyl moieties has led to the selective accumulation of anionic chloro-complexes of HgII in acidic medium in the presence of high chloride concentration and to the uptake of HgII hydroxide around neutral pH, while HgCl2 cannot be adsorbed on this material. The former reaction involves electrostatic interactions between HgCl42− or HgCl3 and the ammonium form of polysiloxane-immobilized amine ligands, and the latter is driven by complexation of HgII species to the unprotonated amine groups. The interest of electrochemistry at carbon paste electrodes modified with these adsorbents for characterizing the sorption processes was also described by applying the following sequence “voltammetric detection subsequent to open-circuit accumulation”. This approach allows the in situ determination of the amount of mercury in the organic-inorganic hybrid phase, as a function of speciation in solution and without significant modification in the solution-phase concentrations, so that the adsorption and ion-exchange isotherms can be obtained very easily and without requiring additional treatment of the solid material.  相似文献   

10.
Single crystals of the hitherto unknown compound Hg2(OH)(NO3)·HgO were obtained unintentionally during hydrothermal phase formation experiments in the system Ag—Hg— As—O. Hg2(OH)(NO3)·HgO (orthorhombic, Pbca, Z = 8, a = 6.4352(8), b = 11.3609(14), c = 15.958(2) Å, 1693 structure factors, 83 parameters, R1[F2 > 2σ(F2)] = 0.0431) adopts a new structure type and is composed of two types of mercury‐oxygen zig‐zag‐chains running perpendicular to each other and of intermediate nitrate groups. One type of chains runs parallel [010] and consists of (Hg—Hg—OH) units with a typical Hg—Hg distance of 2.5143(10) Å for the mercury dumbbell, whereas the other type of chains runs parallel [100] and is made up of (O—Hg—O) units with short Hg—O distances of about 2.02Å. Both types of chains are concatenated by a common O atom with a slightly longer Hg—O distance of 2.25Å. The three‐dimensional assembly is completed by nitrate groups whose O atoms show Hg—O distances > 2.80Å. Weak hydrogen bonding between the OH group and one oxygen atom belonging to the nitrate group stabilizes this arrangement. Hg2(OH)(NO3)·HgO decomposes above 200 °C to HgO.  相似文献   

11.
A field-adapted procedure based on species-specific isotope dilution (SSID) methodology for trace-level determinations of methyl mercury (CH3Hg+) in mire, fresh and sea water samples was developed, validated and applied in a field study. In the field study, mire water samples were filtered, standardised volumetrically with isotopically enriched CH3200Hg+, and frozen on dry ice. The samples were derivatised in the laboratory without further pre-treatment using sodium tetraethyl borate (NaB(C2H5)4) and the ethylated methyl mercury was purge-trapped on Tenax columns. The analyte was thermo-desorbed onto a GC-ICP-MS system for analysis. Investigations preceding field application of the method showed that when using SSID, for all tested matrices, identical results were obtained between samples that were freeze-preserved or analysed unpreserved. For DOC-rich samples (mire water) additional experiments showed no difference in CH3Hg+ concentration between samples that were derivatised without pre-treatment or after liquid extraction. Extractions of samples for matrix–analyte separation prior to derivatisation are therefore not necessary. No formation of CH3Hg+ was observed during sample storage and treatment when spiking samples with 198Hg2+. Total uncertainty budgets for the field application of the method showed that for analyte concentrations higher than 1.5 pg g–1 (as Hg) the relative expanded uncertainty (REU) was approximately 5% and dominated by the uncertainty in the isotope standard concentration. Below 0.5 pg g–1 (as Hg), the REU was >10% and dominated by variations in the field blank. The uncertainty of the method is sufficiently low to accurately determine CH3Hg+ concentrations at trace levels. The detection limit was determined to be 4 fg g–1 (as Hg) based on replicate analyses of laboratory blanks. The described procedure is reliable, considerably faster and simplified compared to non-SSID methods and thereby very suitable for routine applications of CH3Hg+ speciation analysis in a wide range of water samples.  相似文献   

12.
The increasing industrial use of platinum-group elements (PGEs), namely Ir, Pd, Pt and Rh, and related allergies such as rhinitis, conjunctivitis, asthma, urticaria and contact dermatitis, have led to a growing need to monitor selected populations of exposed workers. In this study, the levels of PGEs were measured in indoor airborne particulate matter and in biological samples taken from employees of a plant where car catalytic converters are produced and precious metals are recovered from spent carbon catalysts. The development of an analytical procedure based on quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) for the analysis of PGEs in airborne particulate matter and on sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) for the analysis of PGEs in blood, serum, urine and hair is described. For airborne particulate matter deposited on filters, the limits of detection (LoDs) were found to be 0.006 ng m−3, 0.020 ng m−3, 0.018 ng m−3 and 0.006 ng m−3 for Ir, Pd, Pt and Rh, respectively. Repeatability of measurements ranged from 1.8 to 8.5%, while recovery was in the range from 92 to 102%. For biological samples LoDs in blood, serum, urine and hair ranged from (in ng l−1) 0.2–0.6 for Ir, 5–10 for Pd, 1–3 for Pt and 2–3 for Rh. For all biological materials, the repeatability varied from 1.1 to 12% for the four elements. Recovery data for the determination of PGEs in biological matrices were found to range from 84.0 to 107.8%. The method was applied to the determination of either total or respirable airborne PGEs collected from five different work areas in the plant. The difference between areas with high and low exposure correlates closely with metal levels in hair, blood and urine. The correlation coefficients between Pt in airborne particulate matter and Pt in biological materials was 0.994, 0.991 and 0.970 for blood, hair and urine, respectively.  相似文献   

13.
The titration of chloride with Hg+2 according to CLARKE allows the determination of lower concentrations as was possible according to MOHR. The greater sharpness of the endpoint at lower concentrations and the use of a more dilute Hg+2 solution permit a further lowering of the concentration limit down to 0.05 mg Cl-/l, when using a calibration curve, the remarkable form of which perhaps may be attributed to the formation of HgCl2.2HgO. This sensibility allows a suitable chloride determination in boiler condensates and the wetness determination of steam.  相似文献   

14.
Chitosan and pectic acid have been modeled as disaccharides or oligosaccharides for Hg2+ and Pb2+ adsorption. Reasonable models of both biopolymers were used. Several adsorption sites of both polysaccharides were considered, mainly NH2 in chitosan and CO2 in pectic acid. Hg2+ has several points of anchorage on chitosan. The most important one is NH2 . The Molecular Mechanic modeling permit us to compare in relative terms the different conformations of models of pectic acid and chitosan and their effect in heavy metal coordination. Using the Parameterized Model version 3 (PM3), we report the formation enthalpy of inter‐ and intramolecular compounds with Hg and Pb. The Extended Huckel method (EHM) results seem to indicate that electrostatic interaction (leading to adsorbed cation on NH2 and on sites different to NH2) could be the reason for the high uptake found for Hg2+ using chitosan. Besides NH2, the OH near the amine group is the preferred site for Hg2+ adsorption, especially if it is ionized. In the case of Pb2+ adsorption, several sites of chitosan present no interaction with this cation. Only the NH2 group and the ionized OH group mentioned above seem to be the preferred sites, following the EH modified (EHMO) results. The Hg‐ and Pb‐adsorption modeling on pectic acid permit us to conclude that the best site is the same for both metals: the bridge oxygen between monomers of galacturonic acid. the carbonyl group from carboxylate is the best second site for Hg2+, whereas the internal oxygen bridge is the best second site for Pb2+. Considering the Hg 2+ chemistry in aqueous solution, we evaluated the HgOH+ and HgCl+ or HgCl3 adsorption on both copolymers, using EHMO. The energetic of adsorption changed on both biopolymers for these species, comparing them with Hg2+.  相似文献   

15.
The aim of this study was to compare the influence and feasibility of two common extracting agents (50% v/v HCl and 50% v/v HNO3) on the leaching of Hg from soils. The solubility of a number of Hg species in each acid solution was evaluated under selected conditions. Most species were quantitatively dissolved in both acids with the exception of HgS. The application of both acid solutions to a soil sample from the Almaden mining area provided different recoveries of Hg: about 5% in 50% v/v HNO3 and 50% in 50% v/v HCl. The following experiments were designed and developed in order to evaluate the matrix influence on HgS solubility and leaching: (1) study of the solubility of HgS in the presence of different potential interfering compounds such as FeCl3, KCl, KI, Fe2O3, CuSO4, FeSO4, MnO2 and NaNO3; (2) study of the recovery of HgS spiked in soil samples; (3) study of the extraction process in soil samples spiked with the critical interfering compounds. Results showed the existence of a greater matrix influence with the HCl solution, since much higher Hg recoveries were obtained with this reagent. In addition, the presence of nitrates and Mn oxides drastically promotes the solubility of HgS in an HCl solution. On the other hand, halide compounds drastically enhanced the extractability of Hg in the HNO3 and they must be considered as potential interfering compounds when this acid solution is used as extracting agent. In summary, neither acid is totally free of matrix effects from common soil constituents; conclusions about mercury mobility resulting from the general application of these extraction procedures must therefore be made with caution.  相似文献   

16.
Qinyu Li  Xuan Xu   《Acta Physico》2007,23(12):1875-1880
In order to study the effects of R group on Fe–Hg interactions and 31P chemical shifts, the structures of mononuclear complexes Fe(CO)3(PPh2R)2 (R=pym:1, fur: 2, py: 3,thi: 4; pym=pyrimidine, fur=furyl, py=pyridine, thi=thiazole) and binuclear complexes [Fe(CO)3(PPh2R)2(HgCl2)] (R=pym: 5, fur: 6, py: 7, thi: 8) were studied using the density functional theory (DFT) PBE0 method. The 31P chemical shifts were calculated by PBE0-GIAO method. Nature bond orbital (NBO) analyses were also performed to explain the nature of the Fe–Hg interactions. The conclusions can be drawn as follows: (1) The complexes with nitrogen donor atoms are more stable than those with O or S atoms. The more N atoms there are, the higher is the stabilility of the complex. (2) The Fe–Hg interactions play a dominant role in the stabilities of the complexes. In 5 or 6, thereisa σ-bond between Fe and Hg atoms. However, in 7 and 8, the Fe–Hg interactions act as σP–FenHg and σC–FenHg delocalization. (3) Through Fe→Hg interactions, there is charge transfer from R groups towards the P, Fe, and Hg atoms, which increases the electron density on P nucleus in binuclear complexes. As a result, compared with their mononuclear complexes, the 31P chemical shifts in binuclear complexes show some reduction.  相似文献   

17.
The new cation-radical salt (EPT)HgCl3 is prepared. Its structure and electrical conductivity are studied. The crystal structure of (EPT)HgCl3 contains (EPT)+ in the chair conformation and trigonal planar HgCl3 packed into organic and inorganic layers alternating along thea axis. Shortened intermolecular contacts join HgCl3 into infinite chains along the c axis (Hg...Cl, 3.289 and 3.387 Å), form stacks (S...S, 3.536 and 3.597 Å) and layers (S...S, 3.427–3.498 Å) of EPT+ cation-radicals, and create cation-anion interactions between neighboring layers in the crystal (Cl...S, 3.396–3.521 Å, Cl...C, 3.360 Å). The configuration of the bonds around Hg in HgCl3 is distorted trigonal planar: Hg-Cl, 2.342(3)–2.449(3) Å, Cl-Hg-Cl, 110.7(1)–137.4(1). The Hg atom lies out of the plane of the Cl atoms by 0.015 Å. The conductivity of (EPT)HgCl3 at 20°C is 300 5·10–2 (·cm)–1. The dependence of conductivity on temperature is semiconducting in nature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2055–2061, September, 1991.  相似文献   

18.
Solid HgCl2 is readily detected at ambient conditions by electron capture in a HePI-MS source. The captured electron occupies the empty 6 s orbital of the Hg atom. The resulting radical-anion HgCl2 ?? can exist as three “flexomers” of different Cl-Hg-Cl angle. The facile in-source formation of HgCl2 ?? and the adduct [HgCl3]–- is exploited to detect other solid Hg compounds by exposing them to an external chloride source, such as HCl, NaCl, or vapors emanating from solid TiCl3. In situ oxidation of Hg2Cl2 with H2O2 generated signals for HgCl2 ?? and [HgCl3] , suggesting that oxidation makes Hg 6 s orbital available for electron capture.
Figure
?  相似文献   

19.
The yeast cells, Saccharomyces cerevisiae, were exposed to Hg2+ ions (10–4M) and SeO2 (2·10–4–10–2M) or Se- methionine (2·10–4M). Instrumental neutron activation analysis (INAA) was used to analyze changes in the Hg, Zn, Fe and Co levels in these cells. When the yeast was incubated in a medium containing 10–3M and 10–2M SeO2, the Hg content of the yeast markedly increased. It was also found that the uptake of Se and Hg influenced the levels of Zn, Fe and Co found in the cells. While the presence of Se-methionine (Se-Met), SeO2 or Hg2+ ions caused increases in the intracellular Zn levels, the combined presence of Hg2+ and SeO2 and their assumed interaction, reduced the efficiency of Se for increasing the Zn content of yeast.  相似文献   

20.
The interaction of inorganic mercury (as HgCl2) with SeO2 and organic Se-compounds is compared. Instrumental neutron activation analysis (INAA) was applied as the analytical method. Organ concentrations of Hg and Se were always significantly higher after simultaneous i. p. injections with HgCl2 and Se-compounds. Especially high abundances of Se and Hg in mice organs were found after simultaneous injection with Se-methionine and HgCl2. We suggest that Hg2+ ions are bonded by selenohydryl groups of the metabolites of injected Se-compounds. Binding yield of Hg2+ ions with metabolites of Se-compounds depends upon the chemical form of injected Se-compounds. Variations in the content of Zn, Co, Fe and Rb were observed in all the investigated organs after a single injection with HgCl2 or Se-compounds. Simultaneous injection with HgCl2 and Se-compounds affects the contents of these elements in comparison with single injections.  相似文献   

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