Mercury Volatilization Research Articles

Formation of Mercuric Sulfide in Soil

Analysis of mercury-contaminated soil from the flood plain of East Fork Poplar Creek (EFPC) in Oak Ridge, TN, using a scanning electron microscope (SEM) with energy- and wavelength X-ray dispersive spectroscopy (EDS/WDS) and a transmission electron microscope (TEM) with select area electron diffraction (SAED) revealed the presence of submicron, crystalline mercuric sulfide (HgS) in the form of metacinnabar. The HgS formed in place after the deposition and burial of mercury-contaminated soils. A reaction path model developed to describe the geochemical evolution of the soil redox conditions during flooding predicted that the resultant pe and pH of the soil would be within the stability range of HgS. The reaction of mercury with other metal sulfides or sulfhydryl groups in the soil may have also contributed to the formation of HgS. The formation of HgS is significant to the remediation efforts at EFPC because the toxicity, leachability, and volatility of mercury in soils is dependent on the solid phase speciation. Because the local hydrogeochemical conditions are not unique, the forma tion of HgS at this site has implications to other environments as well.

EPG 97 Abstracts to be presented at the 7th Meeting of the European Placenta Group 13–17 September, 1997

The present study proposes the use of endophytic fungi for mercury bioremediation in in vitro and host-associated systems. We examined mercury resistance in 32 strains of endophytic fungi grown in culture medium supplemented with toxic metal concentrations. The residual mercury concentrations were quantified after mycelial growth. Aspergillus sp. A31, Curvularia geniculata P1, Lindgomycetaceae P87, and Westerdykella sp. P71 were selected and further tested for mercury bioremediation and bioaccumulation in vitro, as well as for growth promotion of Aeschynomene fluminensis and Zea mays in the presence or absence of the metal. Aspergillus sp. A31, C. geniculata P1, Lindgomycetaceae P87 and Westerdykella sp. P71 removed up to 100% of mercury from the culture medium in a species-dependent manner and they promoted A. fluminensis and Z. mays growth in substrates containing mercury or not (Dunnett's test, p < 0.05). Lindgomycetaceae P87 and C. geniculata P1 are dark septate endophytic fungi that endophytically colonize root cells of their host plants. The increase of host biomass correlated with the reduction of soil mercury concentration due to the metal bioaccumulation in host tissues and its possible volatilization. The soil mercury concentration was decreased by 7.69% and 57.14% in A. fluminensis plants inoculated with Lindgomycetaceae P87 + Aspergillus sp. A31 and Lindgomycetaceae P87, respectively (Dunnet's test, p < 0.05). The resistance mechanisms of mercury volatilization and bioaccumulation in plant tissues mediated by these endophytic fungi can contribute to bioremediation programs. The biochemical and genetic mechanisms involved in bioaccumulation and volatilization need to be elucidated in the future.

Detection of the merA gene and its expression in the environment

Bacterial transformation of mercury in the environment has received much attention owing to the toxicity of both the ionic form and organomercurial compounds. Bacterial resistance to mercury and the role of bacteria in mercury cycling have been widely studied. The genes specifying the required functions for resistance to mercury are organized on the mer operon. Gene probing methodologies have been used for several years to detect specific gene sequences in the environment that are homologous to cloned mer genes. While mer genes have been detected in a wide variety of environments, less is known about the expression of these genes under environmental conditions. We combined new methodologies for recovering specific gene mRNA transcripts and mercury detection with a previously described method for determining biological potential for mercury volatilization to examine the effect of mercury concentrations and nutrient availability on rates of mercury volatilization and merA transcription. Levels of merA-specific transcripts and Hg(II) volatilization were influenced more by microbial activity (as manipulated by nutrient additions) than by the concentration of total mercury. The detection of merA-specific transcripts in some samples that did not reduce Hg(II) suggests that rates of mercury volatilization in the environment may not always be proportional to merA transcription.

Volatilization of mercury from natural water by a broad-spectrum Hg-resistantBacillus pasteurii strain DR2

A broad-spectrum mercury-resistant bacterial strain was isolated from contaminated water and was identified as Bacillus pasteurii strain DR2. It could volatilize Hg-compounds including organomercurials from its growth media. It utilized several aromatic compounds as a sole source of carbon. The bacterial strain eliminated HgCl2 from sterile river water and the presence of benzene, toluene, naphthalene and nitrobenzene at 1 mM concentration in the system increased the rate of mercury volatilization, the volatilization rate being highest with benzene. When 1.7×107 cells of this bacterial strain were added per ml of non-sterile water the bacterial strain volatilized more than 90 percent of mercury from mercuric chloride and organo-mercurials like PMA, thiomersol and methoxy ethyl mercuric chloride (MEMC). In the absence of this bacterial strain the volatilization of PMA and MEMC due to the presence of other Hg-resistant organisms in nonsterile polluted water ranged between 20–25 percent and of HgCl2 was about 40 percent. However, in the presence of B. pasteurii DR2 volatilization of these Hg-compounds from non-sterile water increased by 20–40 percent. In the presence of 1 mM benzene the rate of mercury volatilization was even higher. In all the cases the rate of volatilization was higher in the first seven days than in the next seven days.

Volatilization of mercury by immobilized mercury‐resistant bacterial cells

Highly toxic mercury compounds may come into the environment through the use of mercury compounds as disinfectants for hospital and household purposes, Hg catalyst in industries, burning of coal and petroleum products, mercury‐based pesticides and fungicides used in agriculture, and seed dressings. Toxic effects of mercury can be counteracted by microbial cells through the enzymes mercuric reductase and organomercurial lyase. Immobilized mercury‐resistant bacterial cells of Azotobacter chroococcum could effectively volatilize mercury from mercury‐containing buffer and detoxify mercury compounds. Moreover, the efficiency of mercury volatilization was much greater than with the native cells, as immobilized cells can be reused. Immobilized cells continuously volatilized mercury from mercury‐containing buffer after four consecutive 24 h cycles. The storage stability of immobilized cells was much better than that of the native cells.

Volatilization of mercury by resting mercury-resistant bacterial cells.

The mercuric ion reduction system encoded by the Hg2+ inducible mer operon confers bacterial resistance to mercuric ion. The mer A gene product which is a FAD-containing enzyme catalyzes the reduction of Hg2+ to volatile elemental mercury with the help of intracellular thiols and NADPH as a cofactor (Schottel 1974; Summers and Silver 1978; Fox and Walsh 1982; Misra 1992). Our earlier studies have shown that growing cells of different mercury-resistant bacteria reduce Hg2+ compounds to Hg(O) (Ray et al. 1989; Pahan et al. 1990a; Gachhui et al. 1989). We have also shown the effect of thiol compounds and flavins on mercury-degrading enzyme activities in mercury-resistant bacteria (Pahan et al. 1990b). Here we report that resting cells of mercury-resistant bacteria survive in a buffer system for several hours, synthesize inducible mercury-degrading enzymes and volatilize mercury from a mercury-containing buffer system. We know of no information regarding studies of mercury-degrading enzymes in resting mercury-resistant bacterial cells.

Organomercurial resistance determinants in Pseudomonas K-62 are present on two plasmids.

Pseudomonas strain K-62 was found to contain six plasmids. A mutant derivative cured of the 26-kb plasmid showed a higher sensitivity to mercurials; however, the strain was still able to volatilize them. Loss of the 68-kb plasmid in addition to the 26-kb plasmid abolished the ability of mercury volatilization in this strain and led to a further decrease in the level of mercurial resistance. These results are the first to demonstrate that the organomercurial resistance of Pseudomonas strain K-62 is plasmid-based, and that both the 26- and 68-kb plasmids are required for full expression of the mercurial resistance. Probes specific for the mer genes merA, merB, and merR strongly hybridized with the 26-kb plasmid, but not with the 68-kb plasmid. Two fragments of the 26-kb plasmid that hybridized with the mer genes were cloned and expressed in Escherichia coli. One recombinant plasmid (pMRA17) inducibly encoded a typical broad-spectrum mercurial resistance, whereas the other recombinant plasmid (pMRB01) constitutively conferred hypersensitivity to phenylmercury in the absence of mercuric reductase activity. The results suggest that the two organomercurial lyases in the cells are transcribed from different operator-promoters.

Volatilization of demethylmercury and elemental mercury from river Elbe floodplain soils

It has been shown that an untreated mercury-polluted floodplain soil (containing 10 μg/g per dry weight (d.w.) total Hg and 12 ng/g (d.w.) monomethylmercury compounds (MMM)) of the river Elbe in Northern Germany contains both dimethylmercury (DMM) and elemental mercury (Hg°). This is the first time ever that DMM has been detected in unmodified soils. A novel purge- and-trap-technique involving a sequential thermodesorption-separation of the two species after trapping on a carbon molecular sieve (CMS) has been developed that allows the determination of the two species DMM and Hg° from aqueous solutions or soil samples by GC-CVAFS. The compounds' identities as Hg-species were confirmed by GC-ICP/MS. A DMM-concentration of 740 pg/g (d.w.) was determined in the soil; the Hg°-concentration was found to be at least four times larger, but could not yet be quantified. Since no precautions against losses via evapoartion were taken during sampling and storage, the original concentrations were probably much higher. Both DMM and Hg° are easily purged with N2 from soils as well as from soil suspensions, indicating that the two species may readily evaporate from those soils under natural conditions. The amount of DMM determined in the soil suspension was significantly lower (80 pg/g (d.w.)) compared to that in the original soil sample, suggesting that DMM might not be stable under these conditions. Also, it was shown that in natural samples, MMM can be converted into DMM in the presence of sulfide, at S2−-levels as low as 100 μg/g.

Mercury detoxifying enzymes within endospores of a broad-spectrum mercury resistantBacillus pasteurii strain DR2

Bacillus pasteurii DR2, a broad-spectrum Hg-resistant bacterial strain, exhibited delayed sporulation and less mercury volatilization in the presence of mercury compounds. However, Hg-sensitiveBacillus subtilis sporulated quickly in the presence of HgCl2 and volatilized no mercury. Levels of Hg2+-reductase and organomercurial lyase in the endospores ofBacillus pasteurii DR2 were lower than those in vegetative cells

MerA gene expression in aquatic environments measured by mRNA production and Hg(II) volatilization.

The relationship of merA gene expression (specifying the enzyme mercuric reductase) to mercury volatilization in aquatic microbial communities was investigated with samples collected at a mercury-contaminated freshwater pond, Reality Lake, in Oak Ridge, Tenn. Levels of merA mRNA transcripts and the rate of inorganic mercury [Hg(II)] volatilization were related to the concentration of mercury in the water and to heterotrophic activity in field samples and laboratory incubations of pond water in which microbial heterotrophic activity and Hg(II) concentration were manipulated. Levels of merA-specific mRNA and Hg(II) volatilization were influenced more by microbial metabolic activity than by the concentration of mercury. merA-specific transcripts were detected in some samples which did not reduce Hg(II), suggesting that rates of mercury volatilization in environmental samples may not always be proportional to merA expression.

Mapping mercury vapours in an abandoned cinnabar mining area by azalea ( Azalea indica) leaf trapping

Vapour levels of metallic mercury in the atmosphere of an abandoned mercury mine and distillation plant at Abbadia S. Salvatore (Mount Amiata, Tuscany, Italy) were detected by means of the mercury accumulation rate in leaves of azaleas located in 100 sampling sites. The response of azalea leaves to a constant mercury concentration in the air (30 ng/L) was calibrated in the field, in relation to indoor conditions. No significant methylation of mercury was found to occur in spontaneous vegetation or contaminated azalea samples. The volatilization of mercury at different temperatures and the use of bioconcentrators to detect mercury vapours in contaminated areas is discussed.

DPASV determination of mercury in plant material after a preliminary separation via gas phase and gold trap

A new separation procedure was developed which solves problems of organic interferences in the analysis of mercury traces in environmental matrices using differential pulse anodic stripping voltammetry (DPASV). The separation combines the volatilization of metallic mercury and its absorption on Au-wool, followed by a quantitative anodic dissolution of the mercury into a pure electrolyte solution. This procedure prolongs the analysis time for about 2 min, but offers an interference-free determination of mercury using the standard DPASV method without deterioration of sensitivity and precision. The method was tested with plant reference material olive leaves (BCR No 62).

Bacterial enumeration and mercury volatilization in deep subsurface sediment samples

Bacterial enumeration and mercury volatilization in deep subsurface sediment samples

Volatilization of mercury from lake surfaces

Field studies were performed in Canada (at Eagle Lake in north-western Ontario) during July 1986 and subsequently at four oligotrophic forest lakes in south-western Sweden during 1988 and 1989 to determine the extent of mercury volatilization. The Canadian investigations involved simultaneous measurements of total vapour-phase mercury concentrations in air sampled immediately above the water surface and over land nearby. A diurnal cycle was observed for mercury emissions from Eagle Lake, with day-time volatilization rates significantly larger than night-time rates. The Swedish field measurements employed a flux chamber. This device was used to determine the rates at which volatile mercury species were emitted from the lakes. Volatilization occurred from each of the Swedish forest lakes during the warmer seasons of the year (with near-surface water temperatures in the 13–23°C range). For day-time measurements, volatilization rates were generally 3–10 ng Hg m −2 h −1. Daytime fluxes were, on average, about 2.5-times larger than night-time fluxes. Experiments conducted during the winter season (with water temperatures just above the freezing point) indicated very little, if any, emission of volatile mercury species from the lake surface.

Plasmid mediated metal and antibiotic resistance in marine Pseudomonas.

Pseudomonas sp isolated from the Bay of Bengal (Madras coast) contained a single large plasmid (pMR1) of 146 kb. Plasmid curing was not successful with mitomycin C, sodium dodecyl sulfate, acridine orange, nalidixic acid or heat. Transfer of mercury resistance from marine Pseudomonas to Escherichia coli occurred during mixed culture incubation in liquid broth at 10(-4) to 10(-5) ml(-1). However, transconjugants lacked the plasmid pMR1 and lost their ability to resist mercury. Transformation of pMR1 into E. coli competent cells was successful; however, the efficiency of transformation (1.49 x 10(2)Hgr transformants microsgm-1 pMR1 DNA) was low. E. coli transformants containing the plasmid pMR1 conferred inducible resistance to mercury, arsenic and cadmium compounds similar to the parental strain, but with increased expression. The mercury resistant transformants exhibited mercury volatilization activity. A correlation existed between metal and antibiotic resistance in the plasmid pMR1.

Mercuric reductase activity in the adaptation to cationic mercury, phenyl mercuric acetate and multiple antibiotics of a Gram-negative population isolated from an aerobic fixed-bed reactor

Eighty-eight strains, isolated from an aerobic fixed-bed reactor and identified to the genus level, were examined for resistance to 21 antibiotics, cationic mercury and phenylmercuric acetate. All except three were able to grow on Mueller-Hinton agar plates containing 8 micrograms/ml mercuric chloride, but only 42 exhibited a mercuric reductase and an organomercurial lyase activity. Furthermore, 82 of them were multiply-antibiotic resistant, whereas no positive correlation between this property and cationic mercury volatilization capacity was found. It was concluded that this bacterial community-adapted response to these selective agents, which has been most often shown to be mediated by R plasmids, was the result of two independent phenomena. Moreover, the high percentage of multiple antibiotic and mercury resistance found in this population suggested that simultaneous selections occurred on filters of bacteria which exhibited mucoid colonies and tolerance to these two categories of stress agents.

Atmospheric and Tributary Inputs of Toxic Substances to Lake Erie

This paper reports an evaluation of the input of toxic chemicals to Lake Erie in precipitation, in particle and vapor dry deposition, in the Detroit River, and in other Canadian and U.S. tributaries. Results are shown for 13 toxic chemicals for which all or nearly all of these input pathways could be evaluated. The percentage of direct atmospheric contributions relative to total input to Lake Erie calculated for the 13 species are: PCBs, 26%, PAHs, 21%; benzo-a-pyrene, 66%; hexachlorobenzene, 9%; 2,3,7,8-TCDD, 2%; 2,3,7,8-TCDF, 38%; mercury, 22%; lead, 23%; cadmium, 59%; chromium, 17%; arsenic, 8%; dieldrin, 34%; DDT, 29%. For most species the Detroit River was the major input pathway. Vapor phase fluxes out of the lake are indicated for mercury, and for several organic chemicals. Volatilization of PCBs, DDT, and mercury out of the lake is reduced in winter relative to summer, and the vapor flux of PAHs changes direction from volatilization in summer to deposition in winter. The main conclusion of this study is that atmospheric input to Lake Erie may be a significant contributor of certain toxic chemicals.

Mercury removal by immobilized algae in batch culture systems

The accumulation and volatilization of mercury by non-immobilized and immobilizedChlorella emersonii have been studied in batch culture systems. Reduction in the mercury concentration in the growth medium by non-immobilized cells was highly dependent on inoculum density, whilst reduction in mercury concentration by immobilized cells was rapid at all inoculum densities. Mercury accumulation by immobilized cell biomass was significantly greater than by non-immobilized cells with 106 and 105 cells bead−1 or ml−1. Volatilization of mercury by non-immobilized cell systems was greatest at higher inoculum densities, whereas more mercury was volatilized from immobilized cell systems at lower inoculum densities, and was greatest with unstocked alginate beads. Thus, in immobilized systems, mercury removal from solution is complex and involves mercury accumulation by the cells and volatilization by the matrix and cells. Further studies of mercury accumulation and volatilization by unstocked immobilization matrices revealed that agarose volatilized much less mercury than alginate or agar. The precise mechanism of mercury volatilization by alginate remains unclear, though it is thought to be a chemical effect.

Constitutive synthesis of a transport function encoded by the Thiobacillus ferrooxidans merC gene cloned in Escherichia coli

Mercuric reductase activity determined by the Thiobacillus ferrooxidans merA gene (cloned and expressed constitutively in Escherichia coli) was measured by volatilization of 203Hg2+. (The absence of a merR regulatory gene in the cloned Thiobacillus mer determinant provides a basis for the constitutive synthesis of this system.) In the absence of the Thiobacillus merC transport gene, the mercury volatilization activity was cryptic and was not seen with whole cells but only with sonication-disrupted cells. The Thiobacillus merC transport function was compared with transport via the merT-merP system of plasmid pDU1358. Both systems, cloned and expressed in E. coli, governed enhanced uptake of 203Hg2+ in a temperature- and concentration-dependent fashion. Uptake via MerT-MerP was greater and conferred greater hypersensitivity to Hg2+ than did uptake with MerC. Mercury uptake was inhibited by N-ethylmaleimide but not by EDTA. Ag+ salts inhibited mercury uptake by the MerT-MerP system but did not inhibit uptake via MerC. Radioactive mercury accumulated by the MerT-MerP and by the MerC systems was exchangeable with nonradioactive Hg2+.

Solidification of hazardous substances‐a TGA and FTIR study of Portland cement containing metal nitrates

Abstract Type I Portland cement samples containing the soluble nitrates of the priority pollutant metals chromium, lead, barium, mercury, cadmium and zinc have been investigated using thermogravimetric and fourier—transform infrared techniques (including diffuse reflectance). The major vibrational bands and thermal stability of the carbonate, sulfate, silicate, water and nitrate species are tabulated and discussed in comparison to uncontaminated Portland cement. The solubility and volatility of mercury in cement and the effect of metal nitrate concentration on the silicate condensation process is discussed. Although results suggest that retardation of cement setting by Zn and Pb salts occurs by limiting hydration, the chemistry of the two processes is distinctly different.