Microbial reduction of metals and radionuclides

The microbial reduction of metals has attracted recent interest as these transformations can play crucial roles in the cycling of both inorganic and organic species in a range of environments and, if harnessed, may offer the basis for a wide range of innovative biotechnological processes. Under certain conditions, however, microbial metal reduction can also mobilise toxic metals with potentially calamitous effects on human health. This review focuses on recent research on the reduction of a wide range of metals including Fe(III), Mn(IV) and other more toxic metals such as Cr(VI), Hg(II), Co(III), Pd(II), Au(III), Ag(I), Mo(VI) and V(V). The reduction of metalloids including As(V) and Se(VI) and radionuclides including U(VI), Np(V) and Tc(VII) is also reviewed. Rapid advances over the last decade have resulted in a detailed understanding of some of these transformations at a molecular level. Where known, the mechanisms of metal reduction are discussed, alongside the environmental impact of such transformations and possible biotechnological applications that could utilise these activities.     

Microbial detoxification of aflatoxin

Yeasts, molds, bacteria, actinomycetes, algae, and fungal spores were screened for their ability to degrade aflatoxin. Some molds and mold spores partially transformed aflatoxin B(1) to new fluorescing compounds. Only one of the bacteria, Flavobacterium (aurantiacum?) NRRL B-184, removed aflatoxin from solution. Both growing and resting cells of B-184 took up toxin irreversibly. Toxin-contaminated milk, oil, peanut butter, peanuts, and corn were completely detoxified, and contaminated soybean was partially detoxified by addition of B-184. Duckling assays showed that detoxification of aflatoxin solutions by B-184 was complete, with no new toxic products being formed.     

Bacterial resistance and detoxification of heavy metals

Microbial cells have resistances to essentially all of the toxic heavy metals of the Periodic Table. In bacterial cells, the genetic determinants of these resistances are frequently found on small extrachromosomal plasmids and transposons. Sometimes the resistances are associated with detoxifying enzymes. This is true for the Hg²⁺ → Hg⁰ reductase, the As³⁺ → As⁵⁺ oxidase and the Cr⁶⁺ → Cr³⁺ reductase. In other cases, such as As⁵⁺, Ag⁺ and Cd²⁺, no change in redox state occurs but, rather, uptake and transport differences accompany resistance determinants. This article summarizes what is known of bacterial metal resistances for which enzymatic detoxification is known to be the mechanism of resistance. The characteristics and functions of the enzymes are described, as well as a summary of the newer DNA sequence analysis (basic science) and bench-scale efforts (applied science) for the mercuric resistance system.     

Microbial detoxification of waste rubber material by wood-rotting fungi

The extensive use of rubber products, mainly tires, and the difficulties to recycle those products, has resulted in world wide environmental problems. Microbial devulcanisation is a promising way to increase the recycling of rubber materials. One obstacle is that several microorganisms tested for devulcanisation are sensitive to rubber additives. A way to overcome this might be to detoxify the rubber material with fungi prior to the devulcanisation. In this study, 15 species of white-rot and brown-rot fungi have been screened with regard to their capacity to degrade an aromatic model compound in the presence of ground waste tire rubber. The most effective fungus, Resinicium bicolor, was used for detoxification of rubber material. Increase in growth of the desulfurising bacterium Thiobacillus ferrooxidans in presence of the rubber treated with Resinicium bicolor compared to untreated rubber demonstrated that detoxification with fungi is possible.     

Microbial metabolism and detoxification of 7,12-dimethylbenz[a]anthracene

Summary Six strains of fungi grown on Sabouraud dextrose broth in the presence of 7,12-dimethylbenz[a]anthracene (DMBA) were surveyed for their ability to metabolize DMBA. Experiments with [¹⁴C]DMBA indicated that the extent of formation of organic-soluble metabolites ranged from 6 to 28% after 5 days of incubation, depending on the organism tested. The yields of water-soluble metabolites also varied, and ranged from 1 to 33% after 5 days.Cunninghamella elegans ATCC 36112 andSyncephalastrum racemosum UT-70 exhibited the highest DMBA-metabolizing activity among the organisms surveyed.S. racemosum metabolized DMBA primarily to 7-hydroxymethyl-12-methylbenz[a]anthracene (7-OHM-12-MBA)_ and 7,12-dihydroxymethylbenz[a]anthracene (7,12-diOHMBA). Minor metabolites included 7-OHM-12-MBA-trans-5,6-, 8,9- and 10,11-dihydrodiols, and glucuronide and sulfate conjugates of phenolic derivatives of DMBA. In contrast, the major DMBA metabolites produced byC. elegans were water-soluble. The predominant organic-soluble metabolites produced byC. elegans included 7-OHM-12-MBA-trans-5,6-, 8,9- and 10,11-dihydrodiols. DMBA-trans-3,4-dihydrodiol was also detected. Circular dichroism spectral analysis revealed that the major enantiomer of the 7-OHM-12-MBA-trans-8,9-dihydrodiol formed by each organism has anS,S absolute configuration, while the major enantiomers of the 5,6-, 10,11- and 3,4-dihydrodiols had anR,R configuration. The mutagenic activity of extracts fromS. racemosum exposed to DMBA were determined inSalmonella typhimurium TA98. The mutagenicity of DMBA decreased by 36% over a period of 5 days as 33% of the compound was metabolized. Comparison of these results with previously reported results in mammalian systems suggests that there are similarities and differences between the fungal and mammalian oxidation of DMBA and that the overall balance of fungal metabolism is towards a detoxification rather than a bioactivation pathway.     

Microbial degradation and detoxification of 2,4-dinitrophenol in aerobic and anoxic processes

A bacterial strain was isolated from a river sediment in Buenos Aires, Argentina, owing to its ability to utilize 2,4-dinitrophenol (2,4-DNP) as the sole carbon, nitrogen and energy source. The strain was identified as Rhodococcus opacus on the basis of its 16S rRNA gene sequence. R. opacus degrades aerobically 0.27 and 0.54 mM within 22 and 28 h, respectively, and releases the nitro groups from 2,4-DNP as nitrites. Aerobic biodegradation processes were performed using a 2-l volume microfermentor at with agitation (200 rpm), and were evaluated by spectrophotometry, high performance liquid chromatography (HPLC) and microbial growth. The absence of 2,4-DNP transformation products was also confirmed by gas chromatography mass spectrometry (GC–MS). As the nitrite released during 2,4-DNP degradation is in addition an environmental toxic agent it was removed by denitrification in an anoxic process. Detoxification was assessed by using luminescent bacteria, algae and seeds toxicity tests. Toxicity was not detected after combining both the aerobic and anoxic processes.     

Microbial interaction with and tolerance of radionuclides: underlying mechanisms and biotechnological applications

Radionuclides (RNs) generated by nuclear and civil industries are released in natural ecosystems and may have a hazardous impact on human health and the environment. RN-polluted environments harbour different microbial species that become highly tolerant of these elements through mechanisms including biosorption, biotransformation, biomineralization and intracellular accumulation. Such microbial–RN interaction processes hold biotechnological potential for the design of bioremediation strategies to deal with several contamination problems. This paper, with its multidisciplinary approach, provides a state-of-the-art review of most research endeavours aimed to elucidate how microbes deal with radionuclides and how they tolerate ionizing radiations. In addition, the most recent findings related to new biotechnological applications of microbes in the bioremediation of radionuclides and in the long-term disposal of nuclear wastes are described and discussed.     

Transport and detoxification systems for transition metals,heavy metals and metalloids in eukaryotic and prokaryotic microbes

Transition metals, heavy metals and metalloids are usually toxic in excess, but a number of transition metals are essential trace elements. In all cells there are mechanisms for metal ion homeostasis that frequently involve a balance between uptake and efflux systems. This review will briefly describe ATP-coupled resistance pumps. ZntA and CadA are bacterial P-type ATPases that confers resistance to Zn(II), Cd(II) and Pb(II). Homologous copper pumps include the Menkes and Wilson disease proteins and CopA, an Escherichia coli pump that confers resistance to Cu(I). For resistance to arsenicals and antimonials there are several different families of transporters. In E. coli the ArsAB ATPase is a novel system that confers resistance to As(III) and Sb(III). Eukaryotic arsenic resistance transporters include Acr3p and Ycf1p of Saccharomyces cerevisiae. These systems provide resistance to arsenite [As(III)]. Arsenate [As(V)] detoxification involves reduction of As(V) to As(III), a process catalyzed by arsenate reductase enzymes. There are three families of arsenate reductases, two found in bacterial systems and a third identified in S. cerevisiae.     

Microbial leaching of metals from sulfide minerals

Microorganisms are important in metal recovery from ores, particularly sulfide ores. Copper, zinc, gold, etc. can be recovered from sulfide ores by microbial leaching. Mineral solubilization is achieved both by 'direct (contact) leaching' by bacteria and by 'indirect leaching' by ferric iron (Fe(3+)) that is regenerated from ferrous iron (Fe(2+)) by bacterial oxidation. Thiobacillus ferrooxidans is the most studied organism in microbial leaching, but other iron- or sulfide/sulfur-oxidizing bacteria as well as archaea are potential microbial agents for metal leaching at high temperature or low pH environment. Oxidation of iron or sulfur can be selectively controlled leading to solubilization of desired metals leaving undesired metals (e.g., Fe) behind. Microbial contribution is obvious even in electrochemistry of galvanic interactions between minerals.     

Binding and detoxification of heavy metals in lower vertebrates with reference to metallothionein

• 1.1. The metabolism of Cu, Zn, Cd and Hg in lower vertebrates is described, using fish as a model.
• 2.2. The main part of this review deals with metallothionein and the role of this protein for the storage and detoxification of these metals.
• 3.3. Factors influencing the bioavailability and probable uptake routes are identified.
• 4.4. The distribution of the metals within the organism is outlined. The distribution between tissues is described and the subcellular distribution discussed with reference to metallothionein.

     

Molecular mechanisms underlying the toxicity and detoxification of trace metals and metalloids in plants

Plants take up a wide range of trace metals/metalloids(hereinafter referred to as trace metals)from the soil,some of which are essential but become toxic at high concentrations(e.g.,Cu,Zn,Ni,Co),while others are non-essential and toxic even at relatively low concentrations(e.g.,As,Cd,Cr,Pb,and Hg). Soil contamination of trace metals is an increasing problem worldwide due to intensifying human activities.Trace metal contamination can cause toxicity and growth inhibition in plants,as well as accum...     

Microbial leaching of metals from solid industrial wastes

Biotechnological applications for metal recovery have played a greater role in recovery of valuable metals from low grade sulfide minerals from the beginning of the middle era till the end of the twentieth century. With depletion of ore/minerals and implementation of stricter environmental rules, microbiological applications for metal recovery have been shifted towards solid industrial wastes. Due to certain restrictions in conventional processes, use of microbes has garnered increased attention. The process is environmentally-friendly, economical and cost-effective. The major microorganisms in recovery of heavy metals are acidophiles that thrive at acidic pH ranging from 2.0–4.0. These microbes aid in dissolving metals by secreting inorganic and organic acids into aqueous media. Some of the well-known acidophilic bacteria such as Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, Leptospirillum ferrooxidans and Sulfolobus spp. are well-studied for bioleaching activity, whereas, fungal species like Penicillium spp. and Aspergillus niger have been thoroughly studied for the same process. This mini-review focuses on the acidophilic microbial diversity and application of those microorganisms toward solid industrial wastes.     

Immobilization of radionuclides and heavy metals through anaerobic bio-oxidation of Fe(II)

Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 microM uranium and 81 microM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 microM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 microM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment.     

Binding and detoxification of heavy metals in lower vertebrates with reference to metallothionein.

1. The metabolism of Cu, Zn, Cd and Hg in lower vertebrates is described, using fish as a model. 2. The main part of this review deals with metallothionein and the role of this protein for the storage and detoxification of these metals. 3. Factors influencing the bioavailability and probable uptake routes are identified. 4. The distribution of the metals within the organism is outlined. The distribution between tissues is described and the subcellular distribution discussed with reference to metallothionein.     

Microbial detoxification of pathotoxin produced by spot blotch pathogen Bipolaris sorokiniana infecting wheat

Bipolaris sorokiniana causes spot blotch in wheat and barley. The pathogen produces toxin (BS-toxin), which is a sesquiterpenoid belonging to eremophilane family. Isolates of Trichoderma spp., Chaetomium globosum and Pseudomonas fluorescens were tested for detoxification of BS-toxin amended in semi-synthetic medium at different concentrations. All the antagonists showed mycelial growth in toxin amended medium but their growth was less in comparison to growth in normal medium. The growth of biocontrol agents decreased with increasing concentration of toxin. Two isolates of C. globosum (Cg1 and Cg2), T.viride (TV5-2) and Pseudomonas fluorescens produced 4.9, 2.9, 3.6 g mycelium and 5.5 × 10⁵ cfu /ml, respectively exhibiting 50% or less reduction in growth in BS-toxin amended medium at 1,000 ppm concentration. The biocontrol agents also reduced the severity of toxin-induced symptoms and electrolyte leakage from the wheat leaf tissues. Among the microbes tested, maximum reduction in electrolyte leakage was observed in C. globosum (Cg2) treated toxin samples. The spectral analysis also showed a remarkable decrease in optical density of Cg2 treated toxin at 294 nm. High Performance Liquid Chromatography (HPLC) analysis showed almost complete degradation of BS-toxin in C. globosum (Cg2) treated samples.     

Microbial detoxification of bifenthrin by a novel yeast and its potential for contaminated soils treatment

Bifenthrin is one the most widespread pollutants and has caused potential effect on aquatic life and human health, yet little is known about microbial degradation in contaminated regions. A novel yeast strain ZS-02, isolated from activated sludge and identified as Candida pelliculosa based on morphology, API test and 18S rDNA gene analysis, was found highly effective in degrading bifenthrin over a wide range of temperatures (20-40 °C) and pH (5-9). On the basis of response surface methodology (RSM), the optimal degradation conditions were determined to be 32.3 °C and pH 7.2. Under these conditions, the yeast completely metabolized bifenthrin (50 mg · L(-1)) within 8 days. This strain utilized bifenthrin as the sole carbon source for growth as well as co-metabolized it in the presence of glucose, and tolerated concentrations as high as 600 mg · L(-1) with a q(max), K(s) and K(i) of 1.7015 day(-1), 86.2259 mg · L(-1) and 187.2340 mg · L(-1), respectively. The yeast first degraded bifenthrin by hydrolysis of the carboxylester linkage to produce cyclopropanecarboxylic acid and 2-methyl-3-biphenylyl methanol. Subsequently, 2-methyl-3-biphenylyl methanol was further transformed by biphenyl cleavage to form 4-trifluoromethoxy phenol, 2-chloro-6-fluoro benzylalcohol, and 3,5-dimethoxy phenol, resulting in its detoxification. Eventually, no persistent accumulative product was detected by gas chromatopraphy-mass spectrometry (GC-MS) analysis. This is the first report of a novel pathway of degradation of bifenthrin by hydrolysis of ester linkage and cleavage of biphenyl in a microorganism. Furthermore, strain ZS-02 degraded a variety of pyrethroids including bifenthrin, cyfluthrin, deltamethrin, fenvalerate, cypermethrin, and fenpropathrin. In different contaminated soils introduced with strain ZS-02, 65-75% of the 50 mg · kg(-1) bifenthrin was eliminated within 10 days, suggesting the yeast could be a promising candidate for remediation of environments affected by bifenthrin. Finally, this is the first described yeast capable of degrading bifenthrin.     

Growth inhibition of Thiobacillus thiooxidans by metals and reductive detoxification of vanadium (V)

Summary Vanadium (V), molybdenum (VI), and chromium (VI) have all been found to inhibit the growth of Thiobacillus thiooxidans ATCC 8085. Exponentially growing cultures of the microorganism effectively reduce vanadium (V) to the relatively inocuous vanadyl ion, vanadium (IV), by a first order process with a half-life of about 10 h. Concentrations above the reducing capacity of the culture subsequently prevent further microbial growth. The growth of T. thiooxidans is also inhibited by both molybdate and chromate which can prevent growth in the concentration range 2 to 5×10^–4M. These metal toxicities may play a role in curtailing the growth of this organism in microbially assisted leaching operations.