Biodegradation of metal cyanides

Chemistry: molecular biology and microbiology – Process of utilizing an enzyme or micro-organism to destroy... – Destruction of hazardous or toxic waste

Reexamination Certificate

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Details

C435S262000, C435S254100, C435S256300, C435S256500, C435S256700, C435S929000, C435S933000, C435S945000

Reexamination Certificate

active

06287847

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the biodegradation of a metal cyanide or a mixture of two or more metal cyanides and particularly an iron cyanide or mixture of iron cyanides.
2. Discussion of the Background
Coal gasification to produce methane gas was common practice across most of Europe, the UK and USA throughout the nineteenth century to the mid 1960s. This process has fallen into general disuse leaving an estimated 5,000 former gasworks contaminated with the by-products of gasification and its subsequent purification These contaminants typically include inorganics such as sulphur and cyanide containing compounds, metals, volatile aromatics, phenolics and poly aromatic hydrocarbons (PAHs). The removal of hydrogen cyanide and hydrogen sulphide, by passing the gas through oxide purifiers containing iron oxide, resulted in the production of spent oxide containing up to 45,000 mg Kg
−1
of cyanide. Most of the cyanide is complexed with iron in the form of compounds such as Prussian Blue (Fe
4
[Fe(CN)
6
]
3
), giving the spent oxide its characteristic blue colour. The solubility of Prussian Blue is strongly dependent on pH. Although highly stable and insoluble at low pH (typical of gasworks soil), above pH 4 the iron cyanide concentrations in groundwater, due to leaching and run-off, may exceed the Dutch maximum tolerated level of 200 &mgr;g L
−1
(equivalent to 1.28×10
−6
mM) (Meeussen et al, 1992). With this consideration Meeussen et al (1992) have determined that all Prussian Blue should be removed before iron cyanide concentrations will fall to a tolerable level. Biological processes where toxic compounds undergo complete mineralisation are often cheaper, and deemed more environmentally aware than chemical processes to remove such toxic chemicals. Isolation of an organism that has the ability to degrade iron cyanide compounds including Prussian Blue is therefore highly desirable.
Stemphylium loti is a pathogenic fungus of the cyanogenic plant birdsfoot trefoil. The fungus has been shown to induce cyan
H
2
O+HCN→HCONH
2
Fry and Millar (1972) also showed that the enzyme has an optimum pH activity range of 7.0 to 9.0.
Cyanide hydratase has since been purified from a number of other fungi including
Fusarium laterium
(Cluness et al, 1993) and
Gloeocercospora sorghi
(Wang and Van Etten, 1992).
The bacterium
Pseudomonas Fluorescens
NCIMB 11764, first isolated by Harris and Knowles (1983a), utilises KCN under nitrogen limiting conditions at neutral conditions in fed batch. The key enzyme in this case is cyanide oxygenase (Harris and Knowles, 1983b), where the cyanide is converted to ammonia which is subsequently utilised in industrial processes.
HCN+O
2
→CO
2
+NH3
Kunz et al (1992) later showed that cyanide hydratase is also present in a
Pseudomonas species,
although its activity is limited to higher concentrations of 20-50 mM cyanide.
A number of bacteria including
Pseudomonas Fluorescens
NCIMB 11764 (Rollinson et al, 1987),
Pseudomonas putida
BCN3 (Silva-Avalos et al, 199x) and
Pseudomonas paucimobilis
mudlock ATCC 39204 (see U.S. Pat. No: 4,461,834 to Mudder and Whitlock), have the ability to utilise moderately strong metal complexed cyanides in the form of nickel cyanide [Ni(CN)
4
21
] in nitrogen limited batch or continuous culture at neutral pH values. Again cyanides oxygenase activity was observed.
Despite the fact that a number of metallo cyanides, including Ni(CN)
4
2−
and Cu(CN)
4
2−
, have been shown to be biodegradable at neutral pHs (around pH7) by bacteria, no preculture of a micro-organism or a mixed culture of micro-organisms has been isolated with the ability to grow on iron cyanides. There is also no documentation of an organism capable of degrading metallo cyanides at a pH below about pH7. Likewise, although a number of fungi have been shown to tolerate cyanide, in the form of HCN, by detoxification using cyanide hydratase, a fungus has never been shown to grow on any metallo cyanide complex at pH7 or otherwise.
SUMMARY OF THE INVENTION
According to one aspect of the present invention, there is a provided a method for biodegrading a metal cyanide or a mixture of two or more metal cyanides comprising causing an organism to grow in a medium containing the cyanide or cyanides with the pH of the medium being 6 or less. Preferably the organism is a fungus.
According to another aspect of the present invention, there is provided a method for biodegrading a metal cyanide or mixture of two or more metal cyanides comprising causing a fungus to grow in a medium containing the cyanide or cyanides with the pH of the medium being 7.5 or less.
According to a further aspect of the present invention, there is provided a method for biodegrading an iron cyanide or mixture of two or more iron cyanides comprising causing a fungus to grow in a medium containing the cyanide or mixture of cyanides.
Preferably the pH of the medium is less than 7.5 and suitably lies between 3 and 6.
According to a still further aspect of the present invention the fungus is
Fusarium solani
(IMI 369371, which has been deposited in CABI Bioscience under the terms of the Budapest Treaty under the Accession number 380003 on Jan. 6, 1999).
According to a yet still further aspect of the present invention the fungus is
Trichoderma polysporum
(IMI 369372, which has been deposited in CABI Bioscience under the terms of the Budapest Treaty under the Accession number 380004 on Jan. 6, 1999).
According to a further different aspect of the present invention the fungus is
Penicillium miczynski
(IMI 370461, which has been deposited in CABI Bioscience under the terms of the Budapest Treaty under the Accession number 380005 on Jan. 6, 1999).
According to a different aspect of the present invention the fungus is
Fusarium oxysporum
(IMI 370462, which has been deposited in CABI Bioscience under the terms of the Budapest Treaty under the Accession number 380006 on Jan. 6, 1999).
According to a still further different aspect of the present invention the fungus is
Scytalidium thermophilum
(IMI 370463, which has been deposited in CABI Bioscience under the terms of the Budapest Treaty under the Accession number 380007 on Jan. 5, 1999).
CABI Bioscience is the successor to the International Mycological Institute (IMI). CABI Bioscience is located at Bakeham Lane, Egham, Surrey TW20 9TY, United Kingdom.


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patent: 82-94781E/44 (1981-01-01), None
patent: 86-067962/10 (1985-08-01), None
Pereira et al. Isolation, selection and characterization of cyanide-degrading fungus from an industrial effluent. International Biodeterioration and Biodegradatin. 1996, vol. 36, No. 1-2, pp. 45-52.

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