Differential uptake of mercury vapor by gramineous c(3) and c(4) plants

The uptake of mercury vapor by six gramineous plant species was compared under uniform conditions using a whole-plant chamber and ²⁰³Hg-labeled mercury at a low atmospheric concentration. Mean Hg uptake by leaves of the C₃ species oats (Avena sativa), barley (Hordeum vulgare), and wheat (Triticum aestivum) was 5 times greater than that by leaves of the C₄ species corn (Zea mays), sorghum (Sorghum bicolor), and crabgrass (Digitaria sanguinalis). Although there was a difference in resistances associated with vapor entry into the leaves, as shown by estimates of gas exchange, the differential uptake by C₃ and C₄ species was largely attributable to internal resistances to Hg vapor binding. The nature of the internal resistances and the site or sites of Hg vapor binding remain unspecified.     

Estimation of whole-plant resistance to gaseous exchange independent of leaf temperature measurement

For studies into the uptake of mercury vapor by wheat (Triticum aestivum), a simple theory and plant chamber were employed to estimate total leaf resistance of whole plants to water vapor exchange. The estimates were independent of leaf temperature, for which mean values were indirectly determined. The approach involved the measurement, at steady-state conditions, of the net change in water vapor flux per unit of leaf surface (Δq_v) in response to a small induced change in absolute humidity (ΔC_a). Assuming that total leaf resistance (r_l) was constant and that change in leaf temperature (T_l) was negligible, total leaf resistance was calculated from the equation, [Formula: see text]     

Optical characteristics and parameters of gas-discharge plasma in a mixture of mercury dibromide vapor with neon

Results are presented from studies of the optical characteristics and parameters of plasma of a dielectric barrier discharge in a mixture of mercury dibromide vapor with neon—the working medium of a non-coaxial exciplex gas-discharge emitter. The electron energy distribution function, the transport characteristics, the specific power losses for electron processes, the electron density and temperature, and the rate constants for the processes of elastic and inelastic electron scattering by the working mixture components are determined as functions of the reduced electric field. The rate constant of the process leading to the formation of exciplex mercury monobromide molecules is found to be 1.6 × 10^?14 m³/s for a reduced electric field of E/N = 15 Td, at which the maximum emission intensity in the blue-green spectral region (λ_max = 502 nm) was observed in this experiment.     

Characteristics of Electron Drift in an Ar–Hg Mixture

The characteristics of electron drift in a mixture of argon with mercury vapor at reduced electric fields of E/N = 1–100 Td are calculated and analyzed with allowance for inelastic collisions. It is shown that even a minor additive of mercury to argon at a level of a fraction of percent substantially affects the discharge parameters, in particular, the characteristics of inelastic processes. The influence of the concentration of mercury vapor in argon on the kinetic characteristics, such as the diffusion and mobility coefficients and ionization frequency, is investigated.     

Long-lived Ar-Hg plasma in the afterglow of a high-current pulsed discharge

High-density (n > 10¹² cm^?3) argon-mercury plasma produced by a short (t ～ 20 μs) high-power pulsed discharge in argon with an admixture of mercury vapor at a discharge current of ～50 A, an argon pressure of ～4 mm Hg, and a mercury vapor pressure of ～10^?3 mm Hg was studied using optical spectroscopy and radio physics methods. It is found that the lifetime of this plasma after the end of the discharge pulse is up to 10^?2 s. It is shown that such an abnormally long lifetime of such an afterglow plasma, as compared to the plasma of an argon discharge without an admixture of mercury vapor, is related to the long residence time of atoms and ions of both argon and mercury in highly excited states due to chemi-ionization processes involving long-lived metastable argon ions. It is suggested that dissociative recombination of highly excited molecular ions of argon play an important role in the transfer of excitation to argon atoms and ions that are close to autoionization states.     

The preparation and properties of a stable mercury derivative of transfer RNAs from Escherichia coli

Further investigations into the properties of the mercury derivative formed by the reaction of 4-thiouridine-containing tRNAs and pentafluorophenylmercury chloride have been carried out. tRNA^fMet (which contains only one 4-thiouridine residue) has been isolated by a one-step column Chromatographic procedure from unfractionated Escherichia coli tRNA and has been shown to react with the mercury compound to give a derivative which has similar properties to those previously reported for the corresponding mercury derivative of tRNA^Tyr which contains two adjacent 4-thiouridine residues. The mercury derivative of tRNA^Tyr appears to be a competitive inhibitor of tRNA^Tyr in the aminoacylation reaction (tRNA^TyrK_m = 0.42 μM, mercury derivative of tRNA^TyrK_i = 0.11 μM). The mercury derivative of Tyr-tRNA^Tyr can be made, but only by the reaction of the mercury compound with the aminoacylated tRNA.     

Effect of Water Vapor on Lyophilized Serratia marcescens and Escherichia coli

Dried Serratia marcescens ATTC 14014 and Escherichia coli ATTC 4157 cells were exposed to various partial pressures of purified water vapor. The colony-forming ability of the S. marcescens was unimpaired when the dried organisms were stored in water-vapor atmosphere such that P/P₀ < 0.55 or P/P₀ = 1.0 (where P is the pressure of the water vapor in contact with the organisms, and P₀ is vapor pressure of pure water at 25 C). During storage under water-vapor atmospheres with P/P₀ between 0.6 and 1.0, the colony-forming ability of the dried S. marcescens was destroyed. The inactivation by water vapor followed the expression — ln N/N₀ = Kt^1/2, where N₀ and N are the number of viable organisms before and after exposure, respectively, t is time, and K is a pseudo constant which is dependent upon the partial pressure of the water vapor at 25 C. Similar results were obtained with dried E. coli. The addition of solutes to the suspending media before freeze-drying was found to influence the stability of the organisms during exposure to water vapor.     

Mercury-tolerant Transgenic Poplars Expressing Two Bacterial Mercury-metabolizing Genes

Mercury is one of the most toxic metals to various organisms, including humans. Genes involved in mercury metabolism have been cloned fromStaphylococcus aureus, and were modified here to be expressed in plants. Transgenic poplars containing both chimeric genes (p35S-merA andp35S-merB) were developed via two rounds of transformation usingnos-nptll andnos-hpt genes as selectable markers. Although expression levels varied among transgenic lines, tolerance to either ionic mercury or organic mercury matched well with the degree of expression revealed by northern hybridization. In culture, these trees were tolerant to 50 μM HgCl₂ and 2 μM CH₃HgCI. Variations in mercury tolerance among the transgenic lines indicates that vigorous selection is required to select the best clones for use in phytoremediation.     

Detoxification of Mercury by Methanobactin from Methylosinus trichosporium OB3b

Many methanotrophs have been shown to synthesize methanobactin, a novel biogenic copper-chelating agent or chalkophore. Methanobactin binds copper via two heterocyclic rings with associated enethiol groups. The structure of methanobactin suggests that it can bind other metals, including mercury. Here we report that methanobactin from Methylosinus trichosporium OB3b does indeed bind mercury when added as HgCl₂ and, in doing so, reduced toxicity associated with Hg(II) for both Alphaproteobacteria methanotrophs, including M. trichosporium OB3b, M. trichosporium OB3b ΔmbnA (a mutant defective in methanobactin production), and Methylocystis sp. strain SB2, and a Gammaproteobacteria methanotroph, Methylomicrobium album BG8. Mercury binding by methanobactin was evident in both the presence and absence of copper, despite the fact that methanobactin had a much higher affinity for copper due to the rapid and irreversible binding of mercury by methanobactin. The formation of a gray precipitate suggested that Hg(II), after being bound by methanobactin, was reduced to Hg(0) but was not volatilized. Rather, mercury remained associated with methanobactin and was also found associated with methanotrophic biomass. It thus appears that although the mercury-methanobactin complex was cell associated, mercury was not removed from methanobactin. The amount of biomass-associated mercury in the presence of methanobactin from M. trichosporium OB3b was greatest for M. trichosporium wild-type strain OB3b and the ΔmbnA mutant and least for M. album BG8, suggesting that methanotrophs may have selective methanobactin uptake systems that may be based on TonB-dependent transporters but that such uptake systems exhibit a degree of infidelity.     

Mercury and osmoregulation in the euryhaline crab,Eriocheir sinensis

This review will focus on cases where it might be possible that the toxicity of the heavy metal mercury results from an interaction with osmoregulatory mechanisms. It is shown that mercury-induced impairment of osmoregulatory capability in the sense of severe modifications of the blood osmotic concentration is more pronounced in brachyuran decapod species adapted to dilute waters. The rationale for considering these effects is based on a comparison between mercury effects on three species of decapod crustaceans exhibiting various degrees of osmoregulation capability: the strong regulator crab Eriocheir sinensis, the weak regulator Carcinus maenas, both of them being euryhaline, and the stenohaline osmoconformer Cancer pagurus. It is established that a synergistic effect exists between salinity and HgCl₂ toxicity in euryhaline species which are hyperregulators in dilute media, that is, E. sinensis and C. maenas only. Depth study of E. sinensis as a model demonstrates that Na⁺ and Cl⁻ permeabilities of the gill epithelium is affected by mercury, as well as the Na⁺ and Cl⁻ active transport processes located at the same level. Evidences are brought showing that mercury drastically disturbs the Na⁺/K⁺ pump and the Cl⁻ channels located in the serosal baso-lateral membranes of the posterior gills.     

Propagation of a surface microwave along the afterglow plasma column of a high-current pulsed discharge

It is demonstrated experimentally that the lifetime of the afterglow plasma of a high-current pulsed discharge in a dielectric tube filled with a mixture of argon with saturated mercury vapor is longer than 1 ms. Such a long lifetime, during which the electron density decreases from 10¹⁴ to 10¹² cm⁻³, is explained by the chemi-ionization of mercury vapor by long-lived metastable argon atoms. During this time, the afterglow plasma can serve as a microwave waveguide for a weakly damped low-noise E ₀-type axisymmetric surface mode, which allows one to use it for transmission of signals in the centimeter wavelength range.     

Mercury Methylation Independent of the Acetyl-Coenzyme A Pathway in Sulfate-Reducing Bacteria

Sulfate-reducing bacteria (SRB) in anoxic waters and sediments are the major producers of methylmercury in aquatic systems. Although a considerable amount of work has addressed the environmental factors that control methylmercury formation and the conditions that control bioavailability of inorganic mercury to SRB, little work has been undertaken analyzing the biochemical mechanism of methylmercury production. The acetyl-coenzyme A (CoA) pathway has been implicated as being key to mercury methylation in one SRB strain, Desulfovibrio desulfuricans LS, but this result has not been extended to other SRB species. To probe whether the acetyl-CoA pathway is the controlling biochemical process for methylmercury production in SRB, five incomplete-oxidizing SRB strains and two Desulfobacter strains that do not use the acetyl-CoA pathway for major carbon metabolism were assayed for methylmercury formation and acetyl-CoA pathway enzyme activities. Three of the SRB strains were also incubated with chloroform to inhibit the acetyl-CoA pathway. So far, all species that have been found to have acetyl-CoA activity are complete oxidizers that require the acetyl-CoA pathway for basic metabolism, as well as methylate mercury. Chloroform inhibits Hg methylation in these species either by blocking the methylating enzyme or by indirect effects on metabolism and growth. However, we have identified four incomplete-oxidizing strains that clearly do not utilize the acetyl-CoA pathway either for metabolism or mercury methylation (as confirmed by the absence of chloroform inhibition). Hg methylation is thus independent of the acetyl-CoA pathway and may not require vitamin B₁₂ in some and perhaps many incomplete-oxidizing SRB strains.     

Partitioning of mercury in aqueous biphasic systems and on ABEC™ resins

Poly(ethylene glycol)-based aqueous biphasic systems (PEG-ABS) can be utilized to separate and recover metal ions in environmental and hydrometallurgical applications. A concurrent study was conducted comparing the partitioning of mercury between aqueous layers in an ABS [Me-PEG-5000/(NH₄)₂SO₄] and partitioning of mercury from aqueous solutions to aqueous biphasic extraction chromatographic (ABEC-5000) resins. In ammonium sulfate solutions, mercury partitions to the salt-rich phase in ABS, but by using halide ion extractants, mercury will partition to the PEG-rich phase after formation of a chloro, bromo or iodo complex. The efficacy of the extractant increases in the order Cl⁻<Br⁻<I⁻. This behavior is also observed using the ABEC resins where halo complexes of mercury will adsorb to the resin from (NH₄)₂SO₄ solutions with retention following the same order. The onset of mercury extraction or adsorption is different for the three extractants, occurring at the lowest extractant concentration for I⁻, followed by Br⁻, and then Cl⁻. Fluoride does not extract mercury. Extraction or adsorption of mercury is improved at the lowest halide concentrations in the presence of sulfuric acid. The addition of sulfuric acid to (NH₄)₂SO₄ solution results in ABEC retention of mercury even in the absence of halide extractant.     

Uptake of mercury vapor by wheat: an assimilation model

Using a whole-plant chamber and ²⁰³Hg-labeled mercury, a quantitative study was made of the effect of environmental parameters on the uptake, by wheat (Triticum aestivum), of metallic mercury vapor, an atmospheric pollutant. Factors were examined in relation to their influence on components of the gas-assimilation model, [Formula: see text]     

Mercury-resistant bacterial strains Pseudomonas and Psychrobacter spp. isolated from sediments of Orbetello Lagoon (Italy) and their possible use in bioremediation processes

This study was aimed to isolate Hg-resistant bacteria from contaminated sediments of the Orbetello Lagoon in Italy and to assess their possible use as biofilms in bioremediation processes. Enrichment cultures prepared from contaminated sediments in the presence of 0.05 mM of mercury and under aerobic conditions allowed the isolation of five heterotrophic bacterial strains. 16S rDNA gene sequencing assigned the isolated strains to the genera Pseudomonas and Psychrobacter. For the first time mercury-resistant bacterial strains belonging to the genus Psychrobacter were evidenced. Minimum inhibitory concentrations in the presence of HgCl₂ and of CH₃HgCl showed high levels of resistance. EC50 values for the isolated bacterial strains in the presence of HgCl₂ and of CH₃HgCl confirmed the adaptation to the metal. Hg-resistant strains ORHg1, ORHg4 and ORHg5 showed the capacity to volatilize inorganic and organic mercury to elemental mercury, and formed biofilms on pumice particles, and were shown to play a role in the removal of mercury from sediment leachates. This study reports isolation and characterization of new Hg-resistant bacterial strains and provides novel insight into their possible use in bioremediation processes of mercury polluted sediments.     

The X-ray crystal structures of [Hg(C6F4OH-p)2OH2] and [Hg(C6H4OMe-p)(O2CC6F4OMe-p)] - Factors influencing supramolecular Hg-O interactions

An X-ray crystal structure has shown that the previously reported bis(p-hydroxytetrafluorophenyl)mercury crystallises as a monohydrate [Hg(C₆F₄OH-p)₂(OH₂)] exhibiting rare coordination of water to a diorganomercurial. The stereochemistry of the three-coordinate mercury is T-shaped with the water coordinated perpendicular to the near linear C-Hg-C unit. The molecules are linked in chains by hydrogen bonding between the hydroxy groups, and the chains into layers by hydrogen bonding between the water oxygen and an OH group. Thermogravimetric analysis shows two water molecules are eliminated together, both the coordinated water and one formed through condensation of the linked -OH groups. In [Hg(p-MeOC₆H₄)(O₂CC₆F₄OMe-p)], molecules with a near linear strongly bonded C-Hg-O arrangement are observed. These are linked into a linear polymer through Hg-O (carboxylate) bridges giving alternate four-membered and eight-membered rings giving mercury overall square planar stereochemistry.     

Effects of methyl mercury at different dose regimes on eggshell formation and some biochemical characteristics of the eggshell gland mucosa of the domestic fowl

Eggshell formation and egg production in domestic fowl were studied following the administration of methyl mercury (two dose regimes: 5 mg daily for 6 consecutive days and 1 mg daily for 50 consecutive days). A daily oral dose of 5 mg of methyl mercury for 6 consecutive days induced significant eggshell thinning and deformation and inhibited egg production. Uptake of ⁴⁵Ca and synthesis of prostaglandins by a homogenate of eggshell gland mucosa from methyl-mercury-treated birds were significantly reduced, as was the calcium content of blood plasma. A daily oral dose of 1 mg of methyl mercury administered for 50 consecutive days also induced eggshell deformation and thinning and reduced egg production. This dose did not, however, have significant effects on the following: ⁴⁵Ca uptake and prostaglandin synthesis by a homogenate of the eggshell gland mucosa; ⁴⁵Ca uptake by a homogenate of duodenal mucosa; the Ca content of the blood plasma, shell gland mucosa or shell gland lumen; the HCO₃⁻ content of the shell gland lumen or the specific gravity of tibia. Methyl mercury added in vitro to a homogenate of eggshell gland mucosa significantly stimulated the synthesis of prostaglandins PGF_2α and PGE₂. Addition of mercury chloride to the same type of preparation stimulated the synthesis of PGF_2α at the expense of thromboxane (T × B₂) synthesis. Administration of 5 mg methyl mercury for 6 consecutive days seemed to reduce the availability of calcium for eggshell formation. This effect could have been due to a direct inhibitory effect of methyl mercury on calcium uptake from the gastrointestinal tract and/or to mobilization of medullary bone. The administration of 1 mg methyl mercury for 50 consecutive days probably induced the reproductive effects by another mechanism. The effects of methyl mercury on avian eggshell formation are quite different from the effects p,p′-DDE exerts on that process.     

Studies on the inhibition of fumarase and malate dehydrogenase by second generation platinum antitumor drugs

Reaction of equimolar amounts of Cd₂I₄(PPr₃)₂ and Hg₂I₄(PPr₃)₂ leads to formation of the complex CdHgI₄(PPr₃)₂. Phosphorus-31 and mercury-199 nmr studies show both phosphines to be co-ordinated to mercury in solution, and a single crystal X-ray analysis confirms the unsymmetrical nature of the complex in the solid state also: I₂Cd(μ-I)₂Hg(PPr₃)₂. The crystals of the complex are monoclinic, space group P2₁/c, with a = 10.694(6), b = 13.794(7), c = 22.415(9) Å, β = 96.25(5)°. The structure was solved via the heavy-atom method and refined to an R value of 0.048 for 3053 observed diffractometer data. The [CdI₂Hg] ring is almost planar and each metal atom is four co-ordinate. The coordination polyhedron about mercury is highly irregular and the large PHgP angle of 152.8(1)° is attributed both to the presence of two strong σ-donor phoshines and to the bridging nature of the halogen atoms attached to mercury. The far-i.r. spectrum of the complex is discussed.     

Ion Transport through Monolayers and Interfacial Films

Ion transport through monolayers and through several molecules of thick films at the mercury/water interface is discussed. The permeability of the monolayer is described by a rate constant, k_c. The permeability of a thin but not monomolecular film is expressed as a function of the thickness of the film, the diffusion coefficient of the permeant in the film, and the distribution coefficient between the film and the bulk of the solution. The rate constant k_c is expressed in terms of absolute rate processes. In the absence of specific interactions, the activation energy is composed of three terms: (a) electrostatic interaction between the permeating ion and the charged monolayer, (b) monolayer compression work of forming a hole for passage of the ions, and (c) energy of boundary line formation between the monolayer and the hole. The contribution of the third term is especially marked in condensed monolayers. Ions are bound weakly to the monolayers of the dipolar ion lecithin, which complicates the transport problem in this system. The retardation of oxygen reduction by the lecithin monolayer is of particular interest.     

Electrocatalytic four-electron reduction of oxygen at the cytochrome c3-adsorbed electrode

The electrocatalytic activity of cytochrome c₃ for the reduction of molecular oxygen was characterized from the studies of the adsorption of cytochrome c₃ and the co-adsorption of cytochrome c₃ with cytochrome c on the mercury electrode by the a.c. polarographic technique. The adsorption of cytochrome c₃ on the mercury electrode is irreversible and is diffusion-controlled. The maximum amount of cytochrome c₃ adsorbed was 0.92 · 10^?11 mol · cm^?2 at ?0.90 V. The amount of cytochrome c₃ in the mixed adsorbed layer with cytochrome c was determined from the differential capacitance measurement. It was shown that the fractional coverage of cytochrome c₃ can be estimated from its bulk concentration and the diffusion coefficient (1.05 · 10^?6 cm² · s^?1). Cytochrome c₃ catalyzes the electrochemical reduction of molecular oxygen from the two-electron pathways via hydrogen peroxide to the four-electron pathway at the mercury electrode in neutral phosphate buffer solution. The catalytic activity varies with the bulk concentration of cytochrome c₃. The highest catalytic activity for the oxygen reduction (no hydrogen peroxide formation) is attained when one-half of the mercury electrode surface is covered by cytochrome c₃. The addition of cytochrome c or bovine serum albumin to the cytochrome c₃ solution inhibits the catalytic activity of cytochrome c₃. The reversible polarographic behavior of cytochrome c₃ through the mixed adsorbed layer of cytochrome c₃ and cytochrome c was also investigated.