Compositions, systems, and methods for extraction of metals from sulfide minerals using siderophores

Abstract

Provided herein are methods, systems, and compositions for degrading minerals. The methods, systems, and compositions provided herein involve the use of siderophores to degrade minerals such as sulfide materials. The methods, systems, and compositions provided herein may be used to release metal from sulfide mineral materials. The methods, systems, and compositions provided herein may further involve collecting, extracting, and / or purifying the metal released from the minerals.

Description

Attorney Docket No. 66122-710.601COMPOSITIONS, SYSTEMS, AND METHODS FOR EXTRACTION OF METALS FROM SULFIDE MINERALS USING SIDEROPHORESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 684,813, filed on August 19, 2024, U.S. Provisional Application No. 63 / 784,504, filed on April 7, 2025, and U.S. Provisional Application No. 63 / 784,856, filed on April 7, 2025, each of which is hereby incorporated by reference in its entirety.BACKGROUND

[0002] Metals such as lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, and rare earth elements have vast industrial applications and are in high demand across various industries. For example, lithium is widely used for energy storage, rechargeable batteries, electronic motors, electric vehicles, air mobility, clean energy, energy storage from solar panels, and other applications. Lithium has pharmaceutical applications, such as in lithium-based bipolar disorder treatments. Currently available sources and technologies for obtaining metals for use in industrial applications and products are limited, inefficient, costly, energy-intensive, and harmful to the environment.SUMMARY

[0003] There is a significant unmet need for compositions, methods, and systems that facilitate access to existing sources of metals, such as to extract and / or collect the metals from their sources, separate them, process them, and make them available for use in various industrial applications and / or products, in a manner that is industrially scalable, efficient, and inexpensive. This is at least in part to meet the demand for such metals in the industrial applications and products in need thereof. Many of the currently available methods and techniques for doing so are limited with respect to efficiency, scalability, and high cost. In many cases, such existing technologies may require performing processes and reactions at high temperatures and pressures that are energy -intensive, costly, and harmful to the environment. The compositions, methods, and systems of the present disclosure address the aforementioned needs and shortcomings, in some aspects, by providing compositions, methods, and systems for extracting, separating, and / or collecting metals from mineral sources, such as mineral materials including solid mineral materials, natural mineral materials, man-made mineral materials, rocks, ores, deposits, and / or other sources in an efficient, inexpensive, and scalable manner. In some cases, the disclosure further providesAttorney Docket No. 66122-710.601 methods and systems for processing the extracted metals and / or using them in a product (e.g., rechargeable batteries). The extracted metal may be processed and turned into an industrial grade metal, battery grade metal, pharmaceutical grade metal, or other useful forms of metals.

[0004] In an aspect, provided herein is a method of extracting a metal from a sulfide mineral material. The method comprises: (a) contacting the sulfide mineral material with a siderophore under reaction conditions such that the metal contained within the sulfide material is solubilized and released; and (b) collecting the released metal, thereby extracting the metal from the sulfide mineral material. In some embodiments, the sulfide mineral material comprises an ore, a rock, a natural sulfide mineral material, a man-made sulfide mineral material, or any combination thereof. In some embodiments, the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. In some embodiments, the sulfide mineral material comprises chalcopyrite. In some embodiments, the sulfide mineral material comprises laterite. In some embodiments, the sulfide mineral material comprises slag. In some embodiments, the siderophore is derived from an organism selected from the group comprising Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof. In some embodiments, the siderophore is selected from the group consisting of: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of pyoverdine, PyoPpC-3B, pyridine-2,6- dithiocarb oxy late, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof. In some embodiments, the siderophore comprises deferoxamine B. In some embodiments, the siderophore comprisesAttorney Docket No. 66122-710.601 deferoxamine E. In some embodiments, the siderophore comprises pyoverdine. In some embodiments, the siderophore comprises pyoverdine or a derivative of pyoverdine. In some embodiments, the siderophore comprises PyoPpC-3B. In some embodiments, the siderophore comprises azotochelin. In some embodiments, the siderophore comprises pyochelin. In some embodiments, the siderophore comprises azotobactin. In some embodiments, the siderophore comprises ornibactin. In some embodiments, the siderophore is extracted from an organism prior to the contacting. In some embodiments, the siderophore is purified from an organism prior to the contacting. In some embodiments, the organism is selected from the group consisting of: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof. In some embodiments, the reaction conditions comprise a temperature from about 10 °C to about 110 °C. In some embodiments, the reaction conditions comprise a temperature from about 20 °C to about 35 °C. In some embodiments, the reaction conditions comprise a pH from about 3 to about 12. In some embodiments, the reaction conditions comprise a pH from about 5 to about 7. In some embodiments, the reaction conditions comprise a pH from about 7 to about 9. In some embodiments, the reaction conditions comprise a pH of about 4. In some embodiments, the reaction conditions comprise a pH of about 6. In some embodiments, the reaction conditions comprise a pH of about 9. In some embodiments, the reaction conditions comprise a weak acid. In some embodiments, the reaction conditions comprise a weak organic acid. In some embodiments, the reaction conditions comprise a buffer. In some embodiments, the reaction conditions comprise an inorganic buffer. In some embodiments, the reaction conditions comprise an organic buffer. In some embodiments, the reaction conditions comprise a citrate buffer. In some embodiments, the sulfide mineral material is treated with an oxidizing agent prior to the contacting the sulfide mineral material with the siderophore, and wherein the oxidizing agent is used as a catalyst. In some embodiments, the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent is used as a catalyst. In some embodiments, the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent comprisesAttorney Docket No. 66122-710.601 pyocyanin, hydrogen peroxide, or sodium hypochlorite. In some embodiments, the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent comprises pyocyanin. In some embodiments, the reaction conditions comprise an inorganic salt. In some embodiments, the inorganic salt comprises sodium chloride. In some embodiments, the reaction is performed with agitation or without agitation. In some embodiments, the contacting is for at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 60 hours, at least about 72 hours, at least about 84 hours, at least about 96 hours, at least about 108 hours, or at least about 120 hours. In some embodiments, the contacting is for at most about at most about 24 hours, at most about 36 hours, at most about 48 hours, at most about 60 hours, at most about 72 hours, at most about 84 hours, at most about 96 hours, at most about 108 hours, or at most about 120 hours. In some embodiments, the contacting is for about 24 hours, about 36 hours, about 48 hours, about 60 hours, about 72 hours, about 84 hours, about 96 hours, about 108 hours, or about 120 hours. In some embodiments, the siderophore facilitates extraction of a metal from the sulfide mineral material by acidolysis, complexolysis, redoxolysis, or any combination thereof. In some embodiments, the metal is selected from the group consisting of: lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, silver, gold, molybdenum, selenium, lead, beryllium, tellurium, and any combination thereof. In some embodiments, the metal comprises lithium. In some embodiments, the metal comprises magnesium. In some embodiments, the metal comprises nickel. In some embodiments, the metal comprises copper. In some embodiments, the metal comprises cobalt. In some embodiments, the metal comprises zinc. In some embodiments, the metal comprises a rare earth element. In some embodiments, the metal comprises gold. In some embodiments, the metal comprises silver. In some embodiments, the metal comprises molybdenum. In some embodiments, the metal comprises selenium. In some embodiments, the metal comprises lead. In some embodiments, the metal comprises beryllium. In some embodiments, the metal comprises tellurium. In some embodiments, the metal is released into a solution. In some embodiments, the method further comprises extracting the metal from the solution. In some embodiments, the method further comprises purifying the metal from the solution, thereby generating a purified metal. In some embodiments, the purified metal has a purity of at least about 80%. In some embodiments, the purified metal has a purity of at least about 90%. In some embodiments, the purified metal has a purity of at least about 95%. In some embodiments, the purified metal has a purity of at least about 99%. In some embodiments, the purified metal has a purity of at least about 99.99%. In some embodiments, the purified metal has a purity of at least aboutAttomey Docket No. 66122-710.60199.999%. In some embodiments, the purified metal is purified lithium. In some embodiments, the purified lithium is industrial grade, battery grade, or pharmaceutical grade. In some embodiments, the method is performed in situ or ex situ. In some embodiments, the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5%, or higher. In some embodiments, the method has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher. In some embodiments, the method is performed in batches. In some embodiments, the method is performed continuously. In some embodiments, the siderophore is produced in a host cell or in a cell-free production system. In some embodiments, the host cell comprises a bacterial cell. In some embodiments, the bacterial cell is selected from the group consisting of a Pseudomonas bacteria, Streptomyces bacteria, and a Azotobacter bacteria. In some embodiments, the Pseudomonas bacteria is selected from the group consisting of Pseudomonas putida, Pseudomonas fluorescens, and Pseudomonas azotoformans . In some embodiments, the Streptomyces bacteria comprises Streptomyces pilosus. In some embodiments,Azotobacter bacteria comprises Azotobacter vinelandii.

[0005] In an aspect, provided herein is a reaction mixture comprising a sulfide mineral material and a siderophore. In some embodiments, the sulfide mineral material and the siderophore are contacted. In some embodiments, the reaction mixture is under reaction conditions. In some embodiments, the contacting results in a metal contained within the sulfide mineral material is solubilized and released. In some embodiments, the metal is collected. In some embodiments, the sulfide mineral material comprises an ore, a rock, a natural sulfide mineral material, a man-made sulfide mineral material, or any combination thereof. In some embodiments, the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. In some embodiments, the sulfide mineral material comprises chalcopyrite. In some embodiments, the sulfide mineral material comprises laterite. In some embodiments, the sulfide mineral material comprises slag. In some embodiments, the siderophore is derived from an organism selected from the group comprising Acinetobacter baumannii, Azotobacter vinelandii, BacillusAttorney Docket No. 66122-710.601 anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91 , Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor,Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof. In some embodiments, the siderophore is selected from the group consisting of aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of pyoverdine, PyoPpC-3B, pyridine-2,6-dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof. In some embodiments, the siderophore comprises deferoxamine B. In some embodiments, the siderophore comprises deferoxamine E. In some embodiments, the siderophore comprises pyoverdine. In some embodiments, the siderophore comprises pyoverdine or a derivative of pyoverdine. In some embodiments, the siderophore comprises PyoPpC-3B. In some embodiments, the siderophore comprises azotochelin. In some embodiments, the siderophore comprises pyochelin. In some embodiments, the siderophore comprises azotobactin. In some embodiments, the siderophore comprises ornibactin. In some embodiments, the siderophore is derived from an organism prior to the contacting. In some embodiments, the siderophore is purified from an organism prior to the contacting. In some embodiments, the organism is selected from the group consisting of: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof. In some embodiments, the reaction conditions comprise a temperature from about 10 °C to about 110 °C. In some embodiments, theAttomey Docket No. 66122-710.601 reaction conditions comprise a temperature from about 20 °C to about 35 °C. In some embodiments, the reaction conditions comprise a pH from about 3 to about 12. In some embodiments, the reaction conditions comprise a pH from about 5 to about 7. In some embodiments, the reaction conditions comprise a pH from about 8 to about 9. In some embodiments, the reaction conditions comprise a pH of about 4. In some embodiments, the reaction conditions comprise a pH of about 6. In some embodiments, the reaction conditions comprise a pH of about 9. In some embodiments, the reaction conditions comprise a weak acid. In some embodiments, the reaction conditions comprise a buffer. In some embodiments, the reaction conditions comprise an inorganic buffer. In some embodiments, the reaction conditions comprise an organic buffer. In some embodiments, the reaction conditions comprise a citrate buffer. In some embodiments, the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent is used as a catalyst. In some embodiments, the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent comprises pyocyanin, hydrogen peroxide, or sodium hypochlorite. In some embodiments, the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent comprises pyocyanin. In some embodiments, the reaction conditions comprise an inorganic salt. In some embodiments, the reaction conditions comprise an inorganic salt, wherein the inorganic salt comprises sodium chloride. In some embodiments, the reaction conditions comprise a weak organic acid. In some embodiments, the reaction is performed with agitation or without agitation. In some embodiments, the contacting is for at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 60 hours, at least about 72 hours, at least about 84 hours, at least about 96 hours, at least about 108 hours, or at least about 120 hours. In some embodiments, the contacting is for at most about at most about 24 hours, at most about 36 hours, at most about 48 hours, at most about 60 hours, at most about 72 hours, at most about 84 hours, at most about 96 hours, at most about 108 hours, or at most about 120 hours. In some embodiments, the contacting is for about 24 hours, about 36 hours, about 48 hours, about 60 hours, about 72 hours, about 84 hours, about 96 hours, about 108 hours, or about 120 hours. In some embodiments, the siderophore facilitates extraction of a metal from the sulfide mineral material by acidolysis, complexolysis, redoxolysis, or any combination thereof. In some embodiments, the metal is selected from the group consisting of: lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, silver, gold, molybdenum, selenium, lead, beryllium, tellurium, and any combination thereof. In some embodiments, the metal comprises lithium. In some embodiments, the metal comprises magnesium. In some embodiments, the metal comprises nickel. In someAttorney Docket No. 66122-710.601 embodiments, the metal comprises copper. In some embodiments, the metal comprises cobalt. In some embodiments, the metal comprises zinc. In some embodiments, the metal comprises a rare earth element. In some embodiments, the metal comprises a rare earth element. In some embodiments, the metal comprises gold. In some embodiments, the metal comprises silver. In some embodiments, the metal comprises molybdenum. In some embodiments, the metal comprises selenium. In some embodiments, the metal comprises lead. In some embodiments, the metal comprises beryllium. In some embodiments, the metal comprises tellurium. In some embodiments, the metal is released into a solution. In some embodiments, the reaction mixture further comprises extracting the metal from the solution. In some embodiments, the reaction mixture further comprises purifying the metal from the solution, thereby generating a purified metal. In some embodiments, the purified metal has a purity of at least about 80%. In some embodiments, the purified metal has a purity of at least about 90%. In some embodiments, the purified metal has a purity of at least about 95%. In some embodiments, the purified metal has a purity of at least about 99%. In some embodiments, the purified metal has a purity of at least about 99.99%. In some embodiments, the purified metal has a purity of at least about 99.999%. In some embodiments, the purified metal is purified lithium. In some embodiments, the purified lithium is industrial grade, battery grade, or pharmaceutical grade. In some embodiments, the reaction mixture is performed in situ or ex situ. In some embodiments, the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5%, or higher. In some embodiments, the reaction mixture has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher. In some embodiments, the siderophore is produced in a host cell or in a cell-free production system. In some embodiments, the host cell comprises a bacterial cell. In some embodiments, the bacterial cell is selected from the group consisting of: a Pseudomonas bacteria, Streptomyces bacteria, and a Azotobacter bacteria. In some embodiments, the Pseudomonas bacteria is selected from the group consisting of: Pseudomonas putida, Pseudomonas fluorescens, and Pseudomonas azotoformans . In some embodiments, the Streptomyces bacteria comprises Streptomyces pilosus. In some embodiments, the Azotobacter bacteria comprises Azotobacter vinelandii.Attorney Docket No. 66122-710.601INCORPORATION BY REFERENCE

[0006] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

[0008] FIG. 1 shows an example workflow according to the methods of the present disclosure.

[0009] FIG. 2 shows a bar graph depicting stability of siderophores as measured by concentration under different extraction temperatures.

[0010] FIG. 3 shows a bar graph depicting stability of siderophores as measured by concentration under different extraction pHs.

[0011] FIG. 4 shows percentage of copper extraction from secondary sulfides using siderophores as disclosed herein.

[0012] FIG. 5 shows percentage of copper extraction from chalcopyrite using siderophores as disclosed herein.DETAILED DESCRIPTION

[0013] Metals such as lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, and rare earth elements have vast applications across various industries and in different products. The demand for such metals continues to increase, and there is an unmet need for efficient technologies to facilitate access to metal sources, and to extract and collect the metals for use in products and industries in need thereof and to meet demand. As an example, lithium is highly in demand for rechargeable batteries which can be used in a variety of products such as electronics, electric motors and electric vehicles, clean energy industry, solar panels, and beyond. As these industries advance and become more prominent in global markets, so does the demand for lithium. Lithium can be found in a number of sources, including in brine, for example, in brine deposits generated as a result ofAttorney Docket No. 66122-710.601 accumulations of saline groundwater enriched in dissolved lithium. However, brine sources of lithium are limited in abundance and can only be found in limited geographical locations, mostly located in South America.

[0014] Another prominent and abundant source of metals is solid mineral material s / sources, rocks, and ores that are commonly available across the world in a diverse range of geographical areas, constituting a major primary source of metals. The currently available technologies for extracting metals from solid mineral materials / sources, rocks, and ores are limited, inefficient, costly, and environmentally harmful. An example of such process is acid leaching or acid roasting which involves contacting a mineral with a strong acid (e.g., sulfuric acid) to extract a metal, such as lithium, from the mineral. Acid leaching / roasting usually requires reaction conditions involving highly acidic pH, high temperatures (e.g., 200 °C and above) and significant energy consumption (e.g., over 6000 megajoules (MJ) per ton of Li2O extracted). This process is expensive, energy-inefficient, and harmful to the environment. Therefore, there is an unmet need for improved compositions, methods, and systems to address these shortcomings.

[0015] Provided herein are compositions, methods, and systems that can efficiently extract metals from sulfide minerals (e.g., natural minerals (e.g., rock, ore, clay)) such as acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof in an efficient, industrially scalable, inexpensive, and environmentally friendly fashion. For example, in some cases, the methods may avoid reaction conditions requiring substances (e.g., highly acidic solvents), high temperatures and pressures, and the like, which may cause harm to the environment and / or increase the cost, energy demands, and / or environmental footprint of the process. In some cases, this is accomplished by performing an reaction on a sulfide with a siderophore to degrade the sulfide, e.g., to extract and separate a metal (e.g., metal ion / atom) therefrom. The methods, compositions, and systems provided herein may be industrially scaled and implemented. For example, in some cases, the reaction may not require temperatures that are significantly higher than room temperature, may not require pressures that are significantly higher than atmospheric pressure, may not require conditions that are highly acidic or highly basic, and may not require other conditions that are environmentally harmful and costly. Instead, in many cases, the reactions of the present disclosure may be efficiently performed in near-ambient temperature, near-atmosphericAttorney Docket No. 66122-710.601 pressure, and / or near-neutral pH conditions, reducing their cost, energy demand, and environmental footprint. The details of such reaction conditions are further elaborated on herein.

[0016] In some cases, the reaction may comprise using one or more siderophores. The reaction may comprise an extraction reaction performed with the aid of one or more siderophores. The siderophore may degrade sulfide mineral material. In some cases, degradation of the sulfide mineral material may facilitate the extraction of a metal from the sulfide mineral material. The siderophore provided herein can be used to degrade, dissolve, and / or depolymerize sulfides, and liberate metals (e.g., metal ions) therefrom at near-ambient temperatures without the need for an energy -intensive, high temperature acid separation process. This process significantly decreases the environmental impact of refining lithium and other metals deposited in sulfides. Provided herein are also siderophore capable for performing such reactions.

[0017] The term “sequence identity” as used herein generally refers to an exact nucleotide-to- nucleotide or amino acid-to-amino acid correspondence of two polynucleotides or polypeptide sequences, respectively. Typically, techniques for determining sequence identity include determining the nucleotide sequence of a polynucleotide and / or determining the amino acid sequence encoded thereby, and comparing these sequences to a second nucleotide or amino acid sequence. Two or more sequences (polynucleotide or amino acid) can be compared by determining their percentage (%) of “sequence identity”. The % of sequence identity of two sequences, whether nucleic acid or amino acid sequences, is the number of exact matches between two aligned sequences divided by the length of the longer sequence and multiplied by 100. Percent sequence identity may also be determined, for example, by comparing sequence information using the advanced BLAST computer program, including version 2.2.9, available from the National Institutes of Health. The BLAST program is based on the alignment method of Karlin and Altschul, Proc. Natl. Acad. Sci. USA, 87:2264-2268 (1990) and as discussed in Altschul, et al., J. Mol. Biol., 215:403-410 (1990); Karlin And Altschul, Proc. Natl. Acad. Sci. USA, 90:5873-5877 (1993); and Altschul et al., Nucleic Acids Res., 25:3389-3402 (1997). The program may be used to determine percent sequence identity over the entire length of the proteins being compared. Default parameters are provided to optimize searches with short query sequences in, for example, with the blastp program. The program also allows use of an SEG filter to mask-off segments of the query sequences as determined by the SEG program of Wootton and Federhen, Computers and Chemistry 17: 149-163 (1993). Ranges of desired degrees of sequence identity areAttorney Docket No. 66122-710.601 approximately 50% to 100% and integer values therebetween. In general, this disclosure encompasses sequences with at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 98% sequence identity with any sequence provided herein.

[0018] The term “about” or “approximately” generally means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean within 1 or more than 1 standard deviation, per the practice in the art. Alternatively, “about” can mean a range of up to 20%, up to 10%, up to 5%, or up to 1% of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude, preferably within 5-fold, and more preferably within 2- fold, of a value. Where particular values are described in the application and claims, unless otherwise stated, the term “about” meaning within an acceptable error range for the particular value should be assumed.

[0019] In an aspect, provided herein is a method of extracting a metal from a sulfide mineral material (e.g., natural sulfide mineral material, man-made sulfide mineral material, rock, ore, clay and / or other kinds of sulfide mineral material). The method may comprise contacting the sulfide mineral material with a siderophore under reaction conditions such that the metal contained within the sulfide mineral material is solubilized and released. The method may further comprise collecting the released metal, thereby extracting the metal from the sulfide mineral material. In some cases, the sulfide mineral material comprises or is a sulfide natural mineral material or a man-made sulfide mineral material. In some cases, the natural sulfide mineral material comprises or is a rock, an ore, or a clay. In some cases, the metal is a metal ion or metal atom. FIG. 1 shows an example workflow according to the embodiments of the present disclosure.

[0020] In some cases, the methods provided herein involve heap leaching. In some cases, the methods involve contacting a sulfide mineral material with a siderophore as described herein. In some cases, the sulfide mineral material is placed on a liner, and the siderophore is added via a drip system to the sulfide mineral material. In some cases, the sulfide mineral material is crushed to a uniform particle size prior to contacting with the siderophore. In some cases, the siderophores may enhance copper dissolution by breaking passivation layers. In some cases, the sulfide mineral material is low-grade chalcopyrite or mixed oxide-sulfide resources.Attorney Docket No. 66122-710.601

[0021] In some cases, the methods provided herein involve contacting smelter slag with siderophores. In some cases, the methods can transform smelter slag into high-value feedstock. In some cases, the methods provided herein allow for recovery of byproducts such as silver, gold, and / or molybdenum.

[0022] In some cases, the methods provided herein involve solvent extraction and electrowinning (SXZEW). Solvent extraction and electrowinning (SXZEW) is a two-stage hydrometallurgical process that first extracts and upgrades copper ions from low-grade leach solutions into a solvent containing a chemical that selectively reacts with and binds the copper in the solvent. The copper is extracted from the solvent with strong aqueous acid which then deposits pure copper onto cathodes using an electrolytic procedure (electrowinning). In some cases, the methods may increase copper concentration in the leachate. In some cases, the methods may reduce impurities, such as iron.

[0023] In some cases, the siderophore comprises activity such as the capability to digest or degrade a sulfide mineral. In some cases, the sulfide mineral material (e.g., rock / ore / clay) comprises a sulfide. Sulfide may comprise any kind of sulfide. In some cases, the sulfide mineral material comprises an acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, hauerite, jamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. In some cases, the sulfide mineral material comprises similar or near-similar unit cell geometries.

[0024] In some cases, the siderophore is derived from an organism selected from the group comprising: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas B10, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.

[0025] In some cases, the siderophore is selected from the group comprising: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinineAttorney Docket No. 66122-710.601C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of pyoverdine, PyoPpC-3B, pyridine-2,6-dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof. In some embodiments, the siderophore comprises pyoverdine. In some embodiments, the siderophore comprises pyoverdine or a derivative of pyoverdine. In some embodiments, the siderophore comprises PyoPpC-3B. In some embodiments, the siderophore comprises deferoxamine E. In some embodiments, the siderophore comprises Deferoxamine B. In some embodiments, the siderophore comprises azotochelin. In some embodiments, the siderophore comprises ornibactin. In some embodiments, the siderophore comprises pyochelin. In some embodiments, the siderophore comprises azotobactin.

[0026] In some cases, the siderophore may degrade, digest, and / or disintegrate the sulfide. As a result, metals, such as in the form of metal ions, metal atoms, or metal precipitates, may be released from the sulfide mineral material (e.g., into a solution). In some cases, the method may comprise collecting the metal or the solution containing the metal. In some cases, the method may comprise separating the metal from the solution. In some cases, the metal may be water soluble. Alternatively or in addition, the metal may precipitate in the solution. The solution may be an aqueous solution comprising water and / or a buffer described anywhere herein.

[0027] The methods of extraction in the present disclosure, such as the siderophore reactions provided herein, may be performed under a set of reaction conditions. In some cases, the reaction conditions may comprise a reaction temperature (e.g., a temperature under which the extraction, or a portion thereof, is performed). In some cases, the reaction temperature is from about 10 to about 110 degrees Celsius (°C). In some cases, the reaction conditions comprise a temperature from about 10 to about 100 °C. ). In some cases, the reaction conditions comprise a temperature from about 10 to about 90 °C. In some cases, the reaction conditions comprise a temperature from about 10 to about 80 °C. In some cases, the reaction conditions comprise a temperature from about 10 to about 70 °C. In some cases, the reaction conditions comprise a temperature from about 10 to about 60 °C. In some cases, the reaction conditions comprise a temperature from about 10 to about 50 °C. In some cases, the reaction conditions comprise a temperature from about 10 to about 35 °C. In some cases, the reaction conditions comprise a temperature from about 10 to about 30 °C. In some cases, the reaction conditions comprise a temperature from about 20 to about 80 °C. In some cases, the reaction conditions comprise a temperature from about 20 to about 70 °C. In some cases, the reaction conditionsAttorney Docket No. 66122-710.601 comprise a temperature from about 20 to about 60 °C. In some cases, the reaction conditions comprise a temperature from about 20 to about 50 °C. In some cases, the reaction conditions comprise a temperature from about 20 to about 35 °C. In some cases, the reaction conditions comprise a temperature from about 20 to about 30 °C. In some cases, the reaction conditions comprise a temperature from about 30 to about 80 °C. In some cases, the reaction conditions comprise a temperature from about 30 to about 70 °C. In some cases, the reaction conditions comprise a temperature from about 30 to about 60 °C. In some cases, the reaction conditions comprise a temperature from about 30 to about 50 °C. In some cases, the reaction conditions comprise a temperature from about 30 to about 40 °C. In some cases, the reaction conditions comprise a temperature from about 30 to about 35 °C. In some cases, the reaction conditions comprise a temperature from about 45 to about 50 °C. In some cases, the methods of the present disclosure may be performed in near-ambient temperatures and / or pressures In some cases, the temperature ranges of the methods of the present disclosure may be significantly lower than temperatures required in acid roasting, (e.g., 200 °C and above). This may reduce the energy requirements of the process performed using the methods of the present disclosure.

[0028] In some cases, the reaction conditions comprise a temperature of about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60 °C. In some cases, the reaction conditions comprise a temperature of about 10 °C. In some cases, the reaction conditions comprise a temperature of about 11 °C. In some cases, the reaction conditions comprise a temperature of about 12 °C. In some cases, the reaction conditions comprise a temperature of about 13 °C. In some cases, the reaction conditions comprise a temperature of about 14 °C. In some cases, the reaction conditions comprise a temperature of about 15 °C. In some cases, the reaction conditions comprise a temperature of about 16 °C. In some cases, the reaction conditions comprise a temperature of about 17 °C. In some cases, the reaction conditions comprise a temperature of about 18 °C. In some cases, the reaction conditions comprise a temperature of about 19 °C. In some cases, the reaction conditions comprise a temperature of about 20 °C. In some cases, the reaction conditions comprise a temperature of about 21 °C. In some cases, the reaction conditions comprise a temperature of about 22 °C. In some cases, the reaction conditions comprise a temperature of about 23 °C. In some cases, the reaction conditions comprise a temperature of about 24 °C. In some cases, the reaction conditions comprise a temperature of about 25 °C. In some cases, the reaction conditions comprise a temperature of about 26 °C. In some cases, the reaction conditionsAttorney Docket No. 66122-710.601 comprise a temperature of about 27 °C. In some cases, the reaction conditions comprise a temperature of about 28 °C. In some cases, the reaction conditions comprise a temperature of about 29 °C. In some cases, the reaction conditions comprise a temperature of about 30 °C. In some cases, the reaction conditions comprise a temperature of about 31 °C. In some cases, the reaction conditions comprise a temperature of about 32 °C. In some cases, the reaction conditions comprise a temperature of about 33 °C. In some cases, the reaction conditions comprise a temperature of about 34 °C. In some cases, the reaction conditions comprise a temperature of about 35 °C. In some cases, the reaction conditions comprise a temperature of about 36 °C. In some cases, the reaction conditions comprise a temperature of about 37 °C. In some cases, the reaction conditions comprise a temperature of about 38 °C. In some cases, the reaction conditions comprise a temperature of about 39 °C. In some cases, the reaction conditions comprise a temperature of about 40 °C. In some cases, the reaction conditions comprise a temperature of about 41 °C. In some cases, the reaction conditions comprise a temperature of about 42 °C. In some cases, the reaction conditions comprise a temperature of about 43 °C. In some cases, the reaction conditions comprise a temperature of about 44 °C. In some cases, the reaction conditions comprise a temperature of about 45 °C. In some cases, the reaction conditions comprise a temperature of about 46 °C. In some cases, the reaction conditions comprise a temperature of about 47 °C. In some cases, the reaction conditions comprise a temperature of about 48 °C. In some cases, the reaction conditions comprise a temperature of about 49 °C. In some cases, the reaction conditions comprise a temperature of about 50 °C. In some cases, the reaction conditions comprise a temperature of about 51 °C. In some cases, the reaction conditions comprise a temperature of about 52 °C. In some cases, the reaction conditions comprise a temperature of about 53 °C. In some cases, the reaction conditions comprise a temperature of about 54 °C. In some cases, the reaction conditions comprise a temperature of about 55 °C. In some cases, the reaction conditions comprise a temperature of about 56 °C. In some cases, the reaction conditions comprise a temperature of about 57 °C. In some cases, the reaction conditions comprise a temperature of about 58 °C. In some cases, the reaction conditions comprise a temperature of about 59 °C. In some cases, the reaction conditions comprise a temperature of about 60 °C.

[0029] In some cases, the extraction is performed at a pH from about, 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2 to 9, 2 to 10, 2 to 11, 2 to 12, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 3 to 9, 3 to 10, 3 to 11, 3 to 12, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 4 to 9, 4 to 10, 4 to 10, 4 to 11, 4 to 12, 5 to 6, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 5 to 11, 5 to 12, 6 to 7, 6 to 8, 6 to 9, 6 to 10, 6 to 11, 6 to12, 7 to 8, 7 to 9, 7 to 10, 7 to 11, 7 to 12, 8 to 9, 8 to 10, 8 to 11, 8 to 12, or 9 to 10. In someAttorney Docket No. 66122-710.601 cases, the extraction is performed at a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some cases, the extraction is performed at a pH of about at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some cases, the extraction is performed at a pH of about at most 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some cases, the extraction is performed at a pH of 2. In some cases, the extraction is performed at a pH of 3. In some cases, the extraction is performed at a pH of 4. In some cases, the extraction is performed at a pH of 5. In some cases, the extraction is performed at a pH of 6. In some cases, the extraction is performed at a pH of 7. In some cases, the extraction is performed at a pH of 8. In some cases, the extraction is performed at a pH of 9. In some cases, the extraction is performed at a pH of 10. In some cases, the extraction is performed at a pH of 11. In some cases, the extraction is performed at a pH of 12. In some cases, the methods of the present disclosure are performed in pH ranges that are substantially neutral, or in other words, not highly / strongly acidic or highly / strongly basic. In some cases, the method of the present disclosure does not comprise a strong acid, such as is used in acid leaching. In some cases, the method of the present disclosure comprises a weak acid. In some cases, the method of the present disclosure comprises a weak organic acid. In some embodiments, the weak acid comprises acetic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, fumaric acid, formic acid, glycolic acid, hydrofluoric acid, lactic acid, malic acid, nitrous acid, oxalic acid, phosphoric acid, propionic acid, pyruvic acid, succinic acid, sulphurous acid, tartaric acid, or any combination thereof.

[0030] In some embodiments, the reaction conditions comprise a buffer. In some embodiments, the buffer comprises citrate buffer, tri s(hydroxymethyl)aminom ethane buffer, 4-(2-hy droxy ethyl)- 1 -piperazineethanesulfonic acid (HEPES) buffer, potassium dihydrogen phosphate buffer, sodium dihydrogen phosphate buffer, sodium phosphate buffer, 4- morpholineethanesulfonic acid buffer, 3-(N-morpholino)propanesulfonic acid (MOPS) buffer, bi s(2-hy droxy ethyl)amino-tris(hydroxymethyl)m ethane buffer, imidazole buffer, sodium bicarbonate buffer, triethylammonium acetate buffer, or any combination thereof. In some embodiments, the buffer comprises citrate buffer. In some embodiments, the extraction of metals from sulfide materials with siderophores as disclosed herein may be greater under conditions that include a buffer (e.g., citrate buffer) as compared to conditions that do not include a buffer. In some embodiments, the presence of a buffer (e.g., citrate buffer) in a reaction as disclosed herein may increase (in some cases, synergistically) the amount of metals extracted or solubilized from sulfide minerals, as compared to a reaction that does not include a buffer. In some cases, the extraction in the presence of the buffer (e.g., citrate buffer) is performed at pH 7-9.Attorney Docket No. 66122-710.601

[0031] In some embodiments, the sulfide material is treated with an oxidizing agent prior to the contacting the sulfide mineral material with the siderophore. In some embodiments, the sulfide material is treated with an oxidizing agent concurrently with the siderophore. In some embodiments, the oxidizing agent is used as a catalyst. In some embodiments, the oxidizing agent is used and regenerated. In some embodiments, the oxidizing agent is not consumed. In some embodiments, the oxidizing agent comprises pyocyanin, hydrogen peroxide, or sodium hypochlorite. In some embodiments, the oxidizing agent comprises pyocyanin. In some embodiments, the oxidizing agent comprises hydrogen peroxide. In some embodiments, the oxidizing agent comprises sodium hypochlorite.

[0032] In some embodiments, the reaction conditions comprise a salt. In some embodiments, the salt is an organic salt. In some embodiments, the salt is an inorganic salt. In some embodiments, the salt is a chloride salt. In some embodiments, the chloride salt comprises sodium chloride. Any salt that is capable of forming hydration rings may be used. In some cases, contacting the sulfide material with a siderophore in the presence of a salt increases the solubility or extraction of metals from sulfide materials as compared to contacting the sulfide material with the siderophore in the absence of the salt. In some cases, the metals that are solubilized or extracted from the sulfide material in the presence of the salt are any metals that can be made soluble by hydration rings, such as silver, gold, divalent charged metals (calcium, magnesium, zinc, iron, manganese, copper, barium, nickel, cobalt, etc.), or uranium. In some cases, the salt may be present in high amount without affecting the activity of the siderophore. In some cases, the salt may present in an amount up to 350 g / L.

[0033] In some embodiments, the methods of the present disclosure are performed with agitation. In some embodiments, the methods of the present disclosure are performed without agitation.

[0034] In some embodiments, the sulfide mineral is contacted with the siderophore for about 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 84, 96, 108, 120 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about at least 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 84, 96, 108, 120 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about at most 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 84, 96, 108, 120 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 8 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 12 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 16 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for aboutAttorney Docket No. 66122-710.60120 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 24 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 28 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 32 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 36 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 40 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 44 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 48 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 52 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 56 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 60 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 64 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 68 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 72 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 84 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 96 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 108 hours. In some embodiments, the sulfide mineral is contacted with the siderophore for about 120 hours.

[0035] In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about at least 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about at most 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 8 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 12 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 16 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 20 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 24 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reactionAttorney Docket No. 66122-710.601 conditions is for about 28 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 32 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 36 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 40 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 44 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 48 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 52 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 56 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 60 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 64 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 68 hours. In some embodiments, contacting the sulfide mineral material with a siderophore under reaction conditions is for about 72 hours.

[0036] In some cases, the methods of the present disclosure are performed on a sulfide mineral material such as acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. The method may be according to the embodiments described anywhere herein. According to the embodiments described anywhere in the present disclosure, in some cases, the siderophore acts on acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, hauerite, jamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. The siderophore and the method of the present disclosure may degrade, digest, or disintegrate the sulfide and extract a metal therefrom.

[0037] In some cases, the siderophores facilitates extraction of the sulfide mineral by acidolysis. In some cases, the siderophores facilitates extraction of the sulfide mineral by complexolysis. In some cases, the siderophores facilitates extraction of the sulfide mineral by redoxolysis. In some cases, the metal is lithium, aluminum, iron, nickel, copper, cobalt,Attorney Docket No. 66122-710.601 manganese, magnesium, zinc, a rare earth element, gold, silver, molybdenum, selenium, lead, beryllium, and / or tellurium. In some cases, the metal is lithium. In some cases, the metal is copper. In some cases, the metal is cobalt. In some cases, the metal is nickel. In some cases, the metal is zinc. In some cases, the metal is a rare earth element. In some embodiments, the metal is gold. In some embodiments, the metal is silver. In some embodiments, the metal is molybdenum. In some embodiments, the metal is selenium. In some embodiments, the metal is lead. In some embodiments, the metal is beryllium. In some embodiments, the metal is tellurium. As a result of degradation and / or disintegration of the sulfide mineral material, the metal may be released and extracted from the sulfide mineral, in some cases, in a solution, in some cases in the form of a metal ion or a metal atom. The solution may be an aqueous solution.

[0038] In some cases, the method comprises extracting the metal from the solution. In some cases, the method comprises purifying the metal from the solution, thereby generating a purified metal, a metal ion, a metal atom, a solid metal complex, a metal precipitate, or any combination thereof. In some cases, the purified metal has a purity of at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 99%, at least about 99.9%, at least about 99.99%, at least about 99.999%, at least about 99.9999%, or higher purity. In some cases, the purified metal is lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, uranium, silver, gold, molybdenum, selenium, lead, beryllium, and / or tellurium. In some cases, the purified metal is industry-grade, battery-grade, and / or pharmaceutical grade. In some cases, the purified metal is industry-grade lithium, battery -grade lithium, and / or pharmaceutical -grade lithium.

[0039] In some embodiments, the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher. In some embodiments, the method has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher.

[0040] In some embodiments, the extraction is performed in batches or continuously. In some embodiments, the extraction is performed in batches. In some embodiments, the extraction is performed in one batch. In some embodiments, the extraction is performed in two batches. In some embodiments, the extraction is performed in three batches. In some embodiments, theAttorney Docket No. 66122-710.601 extraction is performed in four batches. In some embodiments, the extraction is performed in five batches. In some embodiments, the extraction is performed in more than five batches. In some embodiments the extraction is performed continuously.

[0041] In some aspects, the siderophore produced in a host cell or in a cell-free production system. In some cases, the host cell is a bacterial cell or yeast cell. In some embodiments, the bacterial cell comprises a Pseudomonas bacteria, Streptomyces bacteria, or a Azotobacter bacteria. In some cases, the bacterial cell comprises Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus,Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, or Yersinia pestis. In some embodiments, the bacterial cell comprises Pseudomonas putida, Pseudomonas jluorescens, Pseudomonas azotoformans, Streptomyces pilosus, or Azotobacter vinelandii.

[0042] In some embodiments, the siderophore is derived from an organism. In some embodiments, the siderophore is purified from an organism. In some embodiments, the organism comprises Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, or Yersinia pestis. In some embodiments, the organism is Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas azotoformans, Streptomyces pilosus, or Azotobacter vinelandii.

[0043] In some embodiments, the methods of the present disclosure comprise performing a reaction involving a siderophore and a sulfide mineral material, as described throughout the disclosure. In some embodiments, a reaction mixture comprises a sulfide mineral material and a siderophore. The reaction may be performed inside any suitable container. In someAttorney Docket No. 66122-710.601 cases, the reaction may be performed on a rock or ore. In some cases, the sulfide mineral material may be placed inside a container and added to a solution comprising the siderophore, water, a buffer, and / or potential other reagents for performing the reaction. In some cases, the reaction may be performed in one or more of a container, a dish, a beaker, a device, a tank, a reactor, and / or any combination thereof. The containers (e.g., one or more reactors and / or tanks) may be connected to one another to perform one or more reactions according to the embodiments of the present disclosure. The containers may also be reaction units and / or process units each of which may serve a function as part of the method and / or in combination with the method. For example, one or more tanks, reactors, and / or processing units, may be connected to each other with any configuration, such as in series, in parallel, or any combination thereof to perform the method steps such as contact the siderophore with the sulfide mineral, extracting the metal, separating the metal from the solution, purifying the metal, processing the metal, and converting the metal into an industry -grade, battery-grade, or pharmaceutical-grade metal. In some cases, the method further comprises grinding the sulfide mineral material (e.g., rock / ore) prior to performing the reaction (e.g., the degradation). In some cases, the method further comprises using a filtration / chelating system, a precipitation system, a recycle system, or any combination thereof.

[0044] In some cases, the sulfide mineral material (e.g., rock / ore / clay) comprises a sulfide. The sulfide mineral material such as a rock, ore, natural mineral materials, and / or man-made mineral materials may by abundant sources of valuable metals such as lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, rare earth elements, uranium, gold, silver, molybdenum, selenium, lead, beryllium, tellurium, and other metals with vast industrial use and applications. The methods and siderophores of the present disclosure facilitate access to such sources. Sulfide may comprise any kind of sulfide. In some cases, the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, hauerite, jamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. In some cases, the sulfide mineral material comprises similar or near-similar unit cell geometries.

[0045] In some cases, the siderophore is derived from an organism selected from the group comprising: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, MycobacteriumAttorney Docket No. 66122-710.601 tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.

[0046] In some cases, the siderophore is selected from the group comprising: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of pyoverdine, PyoPpC-3B, pyridine-2,6-dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof. In some embodiments, the siderophore comprises pyoverdine. In some embodiments, the siderophore comprises pyoverdine or a derivative of pyoverdine. In some embodiments, the siderophore comprises PyoPpC-3B. In some embodiments, the siderophore comprises deferoxamine E. In some embodiments, the siderophore comprises Deferoxamine B. In some embodiments, the siderophore comprises azotochelin. In some embodiments, the siderophore comprises ornibactin. In some embodiments, the siderophore comprises pyochelin. In some embodiments, the siderophore comprises azotobactin.

[0047] In some cases, the siderophore may degrade, digest, and / or disintegrate the sulfide. As a result, metals, such as in the form of metal ions, metal atoms, or metal precipitates, may be released from the sulfide mineral material (e.g., into a solution). In some cases, the reaction mixture may comprise collecting the metal or the solution containing the metal. In some cases, the reaction mixture may comprise separating the metal from the solution. In some cases, the metal may be water soluble. Alternatively or in addition, the metal may precipitate in the solution. The solution may be an aqueous solution comprising water and / or a buffer described anywhere herein.

[0048] The metal may be extracted from the sulfide mineral material (in some cases a rock or ore) by using the methods and siderophores described anywhere in the present disclosure. In some cases, the reaction mixture comprises a temperature from about 10 to about 110 degrees Celsius (°C). In some cases, the reaction mixture comprises a temperature from about 10 to about 100 °C. In some cases, the reaction mixture comprises a temperature from about 10 to about 90 °C. In some cases, the reaction mixture comprises a temperature from about 10 toAttorney Docket No. 66122-710.601 about 80 °C. In some cases, the reaction mixture comprises a temperature from about 10 to about 70 °C. In some cases, the reaction mixture comprises a temperature from about 10 to about 60 °C. In some cases, the reaction mixture comprises a temperature from about 10 to about 50 °C. In some cases, the reaction mixture comprises a temperature from about 10 to about 35 °C. In some cases, the reaction mixture comprises a temperature from about 10 to about 30 °C. In some cases, the reaction mixture comprises a temperature from about 20 to about 80 °C. In some cases, the reaction mixture comprises a temperature from about 20 to about 70 °C. In some cases, the reaction mixture comprises a temperature from about 20 to about 60 °C. In some cases, the reaction mixture comprises a temperature from about 20 to about 50 °C. In some cases, the reaction mixture comprises a temperature from about 20 to about 35 °C. In some cases, the reaction mixture comprises a temperature from about 20 to about 30 °C. In some cases, the reaction mixture comprises a temperature from about 30 to about 80 °C. In some cases, the reaction mixture comprises a temperature from about 30 to about 70 °C. In some cases, the reaction mixture comprises a temperature from about 30 to about 60 °C. In some cases, the reaction mixture comprises a temperature from about 30 to about 50 °C. In some cases, the reaction mixture comprises a temperature from about 30 to about 40 °C. In some cases, the reaction mixture comprises a temperature from about 30 to about 35 °C. In some cases, the reaction mixture comprises a temperature from about 45 to about 50 °C. In some cases, the methods of the present disclosure may be performed in nearambient temperatures and / or pressures In some cases, the temperature ranges of the methods of the present disclosure may be significantly lower than temperatures required in acid roasting, (e.g., 200 °C and above). This may reduce the energy requirements of the process performed using the methods of the present disclosure.

[0049] In some cases, the reaction mixture comprises a temperature of about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60 °C. In some cases, the reaction mixture comprises a temperature of about 10 °C. In some cases, the reaction mixture comprises a temperature of about 11 °C. In some cases, the reaction mixture comprises a temperature of about 12 °C. In some cases, the reaction mixture comprises a temperature of about 13 °C. In some cases, the reaction mixture comprises a temperature of about 14 °C. In some cases, the reaction mixture comprises a temperature of about 15 °C. In some cases, the reaction mixture comprises a temperature of about 16 °C. In some cases, the reaction mixture comprises a temperature of about 17 °C. In some cases, the reaction mixture comprises a temperature of about 18 °C. In some cases, the reaction mixture comprises aAttorney Docket No. 66122-710.601 temperature of about 19 °C. In some cases, the reaction mixture comprises a temperature of about 20 °C. In some cases, the reaction mixture comprises a temperature of about 21 °C. In some cases, the reaction mixture comprises a temperature of about 22 °C. In some cases, the reaction mixture comprises a temperature of about 23 °C. In some cases, the reaction mixture comprises a temperature of about 24 °C. In some cases, the reaction mixture comprises a temperature of about 25 °C. In some cases, the reaction mixture comprises a temperature of about 26 °C. In some cases, the reaction mixture comprises a temperature of about 27 °C. In some cases, the reaction mixture comprises a temperature of about 28 °C. In some cases, the reaction mixture comprises a temperature of about 29 °C. In some cases, the reaction mixture comprises a temperature of about 30 °C. In some cases, the reaction mixture comprises a temperature of about 31 °C. In some cases, the reaction mixture comprises a temperature of about 32 °C. In some cases, the reaction mixture comprises a temperature of about 33 °C. In some cases, the reaction mixture comprises a temperature of about 34 °C. In some cases, the reaction mixture comprises a temperature of about 35 °C. In some cases, the reaction mixture comprises a temperature of about 36 °C. In some cases, the reaction mixture comprises a temperature of about 37 °C. In some cases, the reaction mixture comprises a temperature of about 38 °C. In some cases, the reaction mixture comprises a temperature of about 39 °C. In some cases, the reaction mixture comprises a temperature of about 40 °C. In some cases, the reaction mixture comprises a temperature of about 41 °C. In some cases, the reaction mixture comprises a temperature of about 42 °C. In some cases, the reaction mixture comprises a temperature of about 43 °C. In some cases, the reaction mixture comprises a temperature of about 44 °C. In some cases, the reaction mixture comprises a temperature of about 45 °C. In some cases, the reaction mixture comprises a temperature of about 46 °C. In some cases, the reaction mixture comprises a temperature of about 47 °C. In some cases, the reaction mixture comprises a temperature of about 48 °C. In some cases, the reaction mixture comprises a temperature of about 49 °C. In some cases, the reaction mixture comprises a temperature of about 50 °C. In some cases, the reaction mixture comprises a temperature of about 51 °C. In some cases, the reaction mixture comprises a temperature of about 52 °C. In some cases, the reaction mixture comprises a temperature of about 53 °C. In some cases, the reaction mixture comprises a temperature of about 54 °C. In some cases, the reaction mixture comprises a temperature of about 55 °C. In some cases, the reaction mixture comprises a temperature of about 56 °C. In some cases, the reaction mixture comprises a temperature of about 57 °C. In some cases, the reaction mixture comprises a temperature of about 58 °C. In some cases, theAttorney Docket No. 66122-710.601 reaction mixture comprises a temperature of about 59 °C. In some cases, the reaction mixture comprises a temperature of about 60 °C.

[0050] In some cases, the reaction mixture comprises a pH from about 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2 to 9, 2 to 10, 2 to 11, 2 to 12, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 3 to 9, 3 to 10, 3 to 11, 3 to 12, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 4 to 9, 4 to 10, 4 to 10, 4 to 11, 4 to 12, 5 to 6, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 5 to 11, 5 to 12, 6 to 7, 6 to 8, 6 to 9, 6 to 10, 6 to 11, 6 to12, 7 to 8, 7 to 9, 7 to 10, 7 to 11, 7 to 12, 8 to 9, 8 to 10, 8 to 11, 8 to 12, or 9 to 10. In some cases, the reaction mixture comprises a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some cases, the reaction mixture comprises a pH of about at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some cases, the reaction mixture comprises a pH of about at most 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some cases, the reaction mixture comprises a pH of 2. In some cases, the reaction mixture comprises a pH of 3. In some cases, the reaction mixture comprises a pH of 4. In some cases, the reaction mixture comprises a pH of 5. In some cases, the reaction mixture comprises a pH of 6. In some cases, the reaction mixture comprises a pH of 7. In some cases, the reaction mixture comprises a pH of 8. In some cases, the reaction mixture comprises a pH of 9. In some cases, the reaction mixture comprises a pH of 10. In some cases, the reaction mixture comprises a pH of 11. In some cases, the reaction mixture comprises a pH of 12. In some cases, the methods of the present disclosure may be performed in pH ranges that are substantially neutral, or in other words, not highly / strongly acidic or highly / strongly basic. In some cases, the reaction mixture of the present disclosure may not comprise a strong acid, such as is used in acid leaching. In some cases, the reaction mixture of the present disclosure comprises a weak acid. In some cases, the reaction mixture of the present disclosure comprises a weak organic acid. In some embodiments, acetic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, fumaric acid, formic acid, glycolic acid, hydrofluoric acid, lactic acid, malic acid, nitrous acid, oxalic acid, phosphoric acid, propionic acid, pyruvic acid, succinic acid, sulphurous acid, tartaric acid, or any combination thereof.

[0051] In some embodiments, the reaction mixture comprises a buffer. In some embodiments, the buffer comprises citrate buffer, tri s(hydroxymethyl)aminom ethane buffer, 4-(2-hy droxy ethyl)- 1 -piperazineethanesulfonic acid buffer, potassium dihydrogen phosphate buffer, sodium dihydrogen phosphate buffer, sodium phosphate buffer, 4- morpholineethanesulfonic acid buffer, 3-(N-morpholino)propanesulfonic acid buffer, bis(2- hydroxyethyl)amino-tris(hydroxymethyl)methane buffer, imidazole buffer, sodium bicarbonate buffer, triethylammonium acetate buffer, or any combination thereof. In some embodiments, the buffer comprises citrate buffer. In some embodiments, the extraction ofAttorney Docket No. 66122-710.601 metals from sulfide materials with siderophores as disclosed herein may be greater under conditions that include a buffer (e.g., citrate buffer) as compared to conditions that do not include a buffer. In some embodiments, the presence of a buffer (e.g., citrate buffer) in a reaction as disclosed herein may increase (in some cases, synergistically) the amount of metals extracted or solubilized from sulfide minerals, as compared to a reaction that does not include a buffer. In some cases, the extraction in the presence of the buffer (e.g., citrate buffer) is performed at pH 7-9.

[0052] In some cases, the reaction mixture comprises an oxidizing agent. In some embodiments the oxidizing agent is used as a catalyst. In some embodiments, the oxidizing agent is used and regenerated. In some embodiments, the oxidizing agent is not consumed. In some embodiments the oxidizing agent comprises pyocyanin, hydrogen peroxide, or sodium hypochlorite. In some embodiments the oxidizing agent comprises pyocyanin. In some embodiments the oxidizing agent comprises hydrogen peroxide. In some embodiments the oxidizing agent comprises sodium hypochlorite.

[0053] In some cases, the reaction mixture comprises a salt. In some embodiments, the salt is an organic salt. In some embodiments, the salt is an inorganic salt. In some embodiments, the salt is a chloride salt. In some embodiments, the chloride salt comprises sodium chloride. Any salt that is capable of forming hydration rings may be used. In some cases, contacting the sulfide material with a siderophore in the presence of a salt increases the solubility or extraction of metals from sulfide materials as compared to contacting the sulfide material with the siderophore in the absence of the salt. In some cases, the metals that are solubilized or extracted from the sulfide material in the presence of the salt are any metals that can be made soluble by hydration rings, such as silver, gold, divalent charged metals (calcium, magnesium, zinc, iron, manganese, copper, barium, nickel, cobalt, etc.), or uranium. In some cases, the salt may be present in high amount without affecting the activity of the siderophore. In some cases, the salt may present in an amount up to 350 g / L. In some embodiments, the reaction mixture of the present disclosure is performed with agitation. In some embodiments, the reaction mixture of the present disclosure is performed without agitation.

[0054] In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction condition is for about 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 84, 96, 108, 120 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about at least 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 84, 96, 108, 120 hours. In some embodiments, contactingAttorney Docket No. 66122-710.601 the sulfide mineral material with a siderophore in the reaction mixture is for about at most 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 84, 96, 108, 120 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 8 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 12 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 16 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 20 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 24 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 28 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 32 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 36 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 40 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 44 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 48 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 52 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 56 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 60 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 64 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 68 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 72 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 84 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 96 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 108 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 120 hours.

[0055] In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction condition is for about 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68,Attorney Docket No. 66122-710.60172 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about at least 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about at most 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 8 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 12 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 16 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 20 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 24 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 28 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 32 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 36 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 40 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 44 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 48 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 52 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 56 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 60 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 64 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 68 hours. In some embodiments, contacting the sulfide mineral material with a siderophore in the reaction mixture is for about 72 hours.

[0056] In some cases, the reaction mixture of the present disclosure comprises a sulfide mineral material such as acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or anyAttorney Docket No. 66122-710.601 combination thereof. The method may be according to the embodiments described anywhere herein. According to the embodiments described anywhere in the present disclosure, in some cases, the siderophore acts on acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, hauerite, jamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof. The siderophore and the method of the present disclosure may degrade, digest, or disintegrate the sulfide and extract a metal therefrom. The sulfide may be an abundant source of valuable metals such as lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, rare earth elements, uranium, gold, silver, molybdenum, selenium, lead, beryllium, tellurium, and other metals with vast industrial use and applications. The methods and siderophores of the present disclosure facilitate access to such sources.

[0057] In some cases, the siderophores facilitates extraction of the sulfide mineral by acidolysis. In some cases, the siderophores facilitates extraction of the sulfide mineral by complexolysis. In some cases, the siderophores facilitates extraction of the sulfide mineral by redoxolysis. In some cases, the metal is lithium, aluminum, iron, nickel, copper, cobalt, manganese, magnesium, zinc, a rare earth element, gold, silver, molybdenum, selenium, lead, beryllium, and / or tellurium. In some cases, the metal is lithium. In some cases, the metal is copper. In some cases, the metal is cobalt. In some cases, the metal is nickel. In some cases, the metal is zinc. In some cases, the metal is a rare earth element. In some cases, the metal is gold. In some cases, the metal is silver. In some cases, the metal is molybdenum. In some cases, the metal is selenium. In some cases, the metal is lead. In some cases, the metal is beryllium. In some cases, the metal is tellurium. As a result of degradation and / or disintegration of the sulfide mineral material, the metal may be released and extracted from the sulfide mineral, in some cases, in a solution, in some cases in the form of a metal ion or a metal atom. The solution may be an aqueous solution.

[0058] In some cases, the reaction mixture results in extracting the metal from the solution. In some cases, the extraction comprises purifying the metal from the solution, thereby generating a purified metal, a metal ion, a metal atom, a solid metal complex, a metal precipitate, or any combination thereof. In some cases, the purified metal has a purity of at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 99%, at least about 99.9%, at least about 99.99%, at least about 99.999%, at least about 99.9999%, or higher purity. In some cases, the purified metal is lithium,Attorney Docket No. 66122-710.601 aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, uranium, gold, silver, molybdenum, selenium, lead, beryllium, and / or tellurium. In some cases, the purified metal is industry -grade, battery-grade, and / or pharmaceutical grade. In some cases, the purified metal is industry-grade lithium, battery-grade lithium, and / or pharmaceutical -grade lithium.

[0059] In some embodiments, the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher. In some embodiments, the method has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher.

[0060] In some aspects, the siderophore produced in a host cell or in a cell -free production system. In some cases, the host cell is a bacterial cell or yeast cell. In some embodiments, the bacterial cell comprises a Pseudomonas bacteria, Streptomyces bacteria, or a Azotobacter bacteria. In some cases, the bacterial cell comprises Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91 , Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas B10, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus,Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, or Yersinia pestis. In some embodiments, the bacterial cell comprises Pseudomonas putida, Pseudomonas jluorescens, Pseudomonas azotoformans, Streptomyces pilosus, or Azotobacter vinelandii.

[0061] In some embodiments, the siderophore is derived from an organism. In some embodiments, the siderophore is purified from an organism. In some embodiments, the organism comprises Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas B10, Pseudomonas fluorescens,Attorney Docket No. 66122-710.601Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, or Yersinia pestis. In some embodiments, the organism is Pseudomonas putida, Pseudomonas fluorescens, Pseudomonas azotoformans, Streptomyces pilosus, or Azotobacter vinelandii.EXAMPLESExample 1: Siderophore stability assay

[0062] The stability of siderophores in various extraction conditions was tested to determine optimal reaction conditions. Siderophores tested were generated from native bacterial sources. Pseudomonas fluorescens was grown under standard conditions. The siderophore pyoverdine (also known as pyoverdin) was purified from a batch of P. fluorescens and lyophilized. To test the stability of the siderophore, the siderophores were subjected to a range of temperature and pH reaction conditions and then were assayed using a Chrome Azurol S (CAS) assay.

[0063] A small sample of pyoverdine was diluted in water and incubated at a set temperature ranging from 40-80 °C at intervals of 10 degrees for ten minutes. After incubation, the pyoverdine was assayed using a CAS assay. The concentration of the CAS product produced by the siderophore was measured at each temperature condition. The results are shown in FIG. 2 and Table 1 below. The results demonstrated stability of the siderophore at a range of temperatures.Table 1. Stability of pyoverdine at various temperatures

[0064] A small sample of pyoverdine was diluted in water and incubated at a set pH ranging from 4.0-10.0 at intervals of 10 degrees for ten minutes. After incubation, the pyoverdine was assayed using a CAS assay. The concentration of the CAS product produced by the siderophore was measured at each pH condition. The results are shown in FIG. 3 and Table 2 below. The results demonstrated stability of the siderophore at a range of pHs.Table 2. Stability of pyoverdine at various temperaturesAttorney Docket No. 66122-710.601Example 2: Extraction of sulfide mineral material with pyoverdine

[0065] Sulfide mineral material comprise metals such as lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, rare earth elements, uranium, and other metals with vast industrial use and applications. However, the currently available technologies for extracting said metals may be limited, inefficient, costly, and environmentally harmful. The methods described herein comprise contacting the sulfide mineral material with a siderophore under reaction conditions such that the metal contained within the sulfide mineral material is solubilized and released in near-ambient temperature, near-atmospheric pressure, and / or nearneutral pH conditions, reducing the cost, energy demand, and environmental footprint of said reaction.

[0066] Pyoverdine is incubated with a sulfide for extraction of metals. The sulfide is crushed into a 40% (w / v) mineral slurry. The reaction mixture comprises a weak organic acid solution at a pH of 4. The reaction mixture is incubated at a temperature of 32 °C for a period of 48-60 hours with agitation. After the incubation period is complete, the reaction mixture is washed with water at a pH of 3.Example 3: Extraction of copper from secondary sulfides using siderophores

[0067] A lab-scale heap leaching test was performed. Secondary sulfides were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores pyoverdin, ornibactin, or pyochelin, for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. Testing for copper extraction was performed using Inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES). As shown in FIG. 4, over lOx more copper extraction using pyochelin was observed as compared to sulfuric acid. This data demonstrates that siderophores can extract copper from mixed oxide-sulfide deposits.Example 4: Extraction of copper from chalcopyrite using siderophores

[0068] A lab-scale heap leaching test was performed. Chalcopyrite was contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores pyoverdin, ornibactin, or pyochelin, for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. Testing for copper extraction was performed using Inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES). As shown in FIG. 5, 5.16% copper was extracted using pyochelin as compared to 0.37% with sulfuric acid. This data demonstrates that siderophores can extract copper from chalcopyrite.Attorney Docket No. 66122-710.601Example 5: Extract value from slag treated with siderophores

[0069] Table 3 depicts extract value from slag for various metals treated with sulfuric acid, or the siderophores pyoverdin, ornibactin, or pyochelin. The data demonstrates that the siderophores were capable of extracting more copper from slag than sulfuric acid. The data also demonstrates that the siderophores were capable of recovering byproducts such as gold, silver, and molybdenum.Table 3. Extract value from slagExample 6: Extract value from ore-grade copper samples treated with siderophores

[0070] A lab-scale heap leaching test was performed. Ore-grade copper samples were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin, for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. After 48 hours, the reaction was stopped, and the samples were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP-OES, with 10 ppm Yttrium as the internal standard. Each sample was measured three times, and the average of these three independent measurements is summarized inAttorney Docket No. 66122-710.601Table 4a. The data demonstrates that the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin were capable of extracting more copper from ore-grade copper samples than sulfuric acid. The data also demonstrates that the siderophores were capable of recovering byproducts such as aluminum, iron, and zinc.Table 4a. Extract value from ore-grade copper samples

[0071] The percentage of copper extracted from the ore-grade copper samples using H2SO4 or the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin is summarized in Table 4bTable 4b. Percentage of copper extracted from ore-grade copper samplesExample 7: Extract value from leach-grade copper samples treated with siderophores

[0072] A lab-scale heap leaching test was performed. Leach-grade copper samples were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin, for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. After 48 h, the reaction was stopped, and the samplesAttorney Docket No. 66122-710.601 were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP- OES, with 10 ppm Yttrium as the internal standard. Each sample was measured three times, and the average of these three independent measurements is summarized in Table 5a. The data demonstrates that the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin were capable of extracting more copper from leach-grade copper samples than sulfuric acid. The data also demonstrates that the siderophores were capable of recovering byproducts such as aluminum, iron, and zinc.Table 5a. Extract value from leach-grade copper samples

[0073] The percentage of the copper extracted from leach-grade copper samples using H2SO4 or the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin is summarized in Table 5bTable 5b. Percentage of copper extracted from leach-grade copper samplesAttorney Docket No. 66122-710.601Example 8: Extract value from chalcopyrite treated with siderophores in the presence of pyocyanin and NaCl

[0074] A lab-scale heap leaching test was performed. Chalcopyrite samples were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores ornibactin, py overdine, or pyochelin, in the presence of 10% pyocyanin and 30 g / L NaCl for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. After 48 hours, the reaction was stopped, and the samples were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP-OES, with 10 ppm Yttrium as the internal standard. Each sample was measured three times, and the average of these three independent measurements is summarized in Table 6a. The data demonstrates that the siderophores pyochelin, ornibactin, or py overdine in the presence of pyocyanin and 30 g / L NaCl were capable of extracting more copper from chalcopyrite than sulfuric acid. The data also demonstrates that the siderophores were capable of recovering byproducts such as zinc.Table 6a. Extract value from chalcopyrite using siderophores in the presence of pyocyanin and NaCl

[0075] The percentage of the copper extracted from chalcopyrite rocks using H2SO4 or the siderophores pyochelin, ornibactin, pyoverdin, or azotobactin in the presence of pyocyanin and 30 g / L of NaCl is summarized in Table 6b.Atorney Docket No. 66122-710.601Table 6b. Percentage of copper extracted from chalcopyrite using siderophores in the presence of pyocyanin and NaClExample 9: Extract value from copper oxide ores treated with siderophores in the presence or absence of NaCl

[0076] A lab-scale heap leaching test was performed. Copper oxide ore samples were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores ornibactin or pyoverdine in the presence or absence of 50 g / L of NaCl for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. The reaction was stopped, and the samples were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP-OES, with 10 ppm Yttrium as the internal standard. Each sample was measured three times, and the average of these three independent measurements is summarized in Table 7a. The data demonstrates that the siderophores ornibactin or pyoverdine in the presence of 50 g / L NaCl were capable of extracting more copper from copper oxide ores than sulfuric acid. Pyoverdine was also capable of extracting more copper from copper oxide ores than sulfuric acid in the absence of 50 g / L NaCl. The data also demonstrates that the siderophores were capable of recovering iron under said in the presence or absence of 50 g / L NaCl.Atorney Docket No. 66122-710.601Table 7a. Extract value from copper oxide ores using siderophores in the presence or absence of NaCl

[0077] The percentage of the copper extracted from copper oxide ores using H2SO4 or the siderophores omibactin or py overdin in the presence of 50 g / L of NaCl is summarized inTable 7bTable 7b. Percentage of copper extracted from copper oxide ores using siderophores in the presence or absence of NaClExample 10: Extract value from sulfide ores with pyoverdine and ornibactin in the presence or absence of NaCl

[0078] A lab-scale heap leaching test was performed. Sulfide ore samples (primary and secondary) were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophores ornibactin or pyoverdine in the presence or absence of 50 g / L of NaCl for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. The reaction was stopped, and the samples were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP-OES, with 10 ppm Yttrium as the internal standard. Each sample was measured three times, and the average of these three independent measurements isAttorney Docket No. 66122-710.601 summarized in Table 8a. The data demonstrates that the siderophores omibactin or pyoverdine in the presence of 50 g / L NaCl were capable of extracting more copper from sulfide ores than sulfuric acid. Pyoverdine was also capable of extracting more copper from sulfide ores than sulfuric acid in the absence of 50 g / L NaCl. The data also demonstrates that the siderophores were capable of recovering iron under said in the presence or absence of 50 g / L NaCl.Table 8a. Extract value from sulfide ores using siderophores in the presence or absence of NaCl

[0079] The percentage of the copper extracted from sulfide ores using H2SO4 or the siderophores omibactin or pyoverdin in the presence or absence of 50 g / L of NaCl is summarized in Table 8b.Table 8b. Percentage of copper extracted from sulfide ores using siderophores in the presence or absence of NaClExample 11: Sequential extraction of copper from sulfide ores with pyoverdine after pretreatment with pyocyanin

[0080] A lab-scale heap leaching test was performed. Copper sulfide ore samples (primary and secondary) were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, orAtorney Docket No. 66122-710.601 the siderophore pyoverdine for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. The copper sulfide ore samples were pretreated with pyocyanin for 2 hours prior to addition of pyoverdine. After 48 hours, the reaction was stopped, and the samples were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP- OES, with 10 ppm Yttrium as the internal standard. This process (including the 2h pretreatment with pyocyanin prior to the addition of pyoverdine) was repeated five times for a total of 240 hour experiment. A 1 mL sample was taken from the liquid fraction of each sample in this study. The percentage of copper extracted after each wash and the total amount of copper extracted after the five washes is summarized in Table 9.Table 9. Percentage of copper extracted from sulfide ores using pyoverdine after pretreatment of the sample with pyocyaninExample 12: Sequential extraction of copper from transition copper ores with ornibactin after pretreatment with pyocyanin

[0081] A lab-scale heap leaching test was performed. Transition copper ore samples were contacted with DI water control, 0.1 M sulfuric acid (H2SO4) control, or the siderophore ornibactin for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. The transition copper ore samples were pretreated with pyocyanin for 2 hours prior to addition of ornibactin. After 48 hours, the reaction was stopped, and the samples were centrifuged at 5000 rpm for 10 min to separate the solid and liquid fractions. A 1 ml sample was taken from the liquid fraction of each sample, diluted with 9 mL of 2% nitric acid solution, filtered using a 0.45 pm PTFE filter, and analyzed on the iCAP PRO XP Duo ICP-OES, with 10 ppm Yttrium as the internal standard. This process (including the 2h pre-treatment with pyocyaninAttorney Docket No. 66122-710.601 prior to the addition of omibactin) was repeated five times for a total of 240 hour experiment. A 1 mL sample was taken from the liquid fraction of each sample in this study. The percentage of copper extracted after each wash and the total amount of copper extracted after the five washes is summarized in Table 10.Table 10. Percentage of copper extracted from T-copper ores using ornibactin after pretreatment of the samples with pyocyaninExample 13: Extraction of copper from slag treated with pyoverdine in the presence of citrate buffer

[0082] A lab-scale heap leaching test was performed. A lab-scale heap leaching test was performed. Copper slag was treated with py overdin in the presence of citrate buffer (pH 8.8) for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. This process was repeated five times for a total of 240 hour experiment. Testing for copper extraction was performed using Inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES). As shown in Table 11, the presence of citrate buffer improved the percentage of copper extracted from copper slag with pyoverdine compared to the extraction carried out in the absence of citrate buffer.Table 11. Percentage of copper extracted from slag using pyoverdine in the presence or absence or citrate bufferAttorney Docket No. 66122-710.601Example 14: Extraction of copper from slag treated with ornibactin in the presence of citrate buffer

[0083] A lab-scale heap leaching test was performed. Copper slag was treated with ornibactin in the presence of citrate buffer (pH 8.8) for 48 hours at 32° C, with 250 rpm agitation, and no heat and no pressure. This process was repeated five times for a total of 240 hour experiment. Testing for copper extraction was performed using Inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES). As shown in Table 12, the presence of citrate buffer improved the percentage of copper extracted from copper slag with ornibactin compared to the extraction carried out in the absence of citrate buffer.Table 12. Percentage of copper extracted from slag using ornibactin in the presence or absence or citrate bufferAttorney Docket No. 66122-710.601CERTAIN EMBODIMENTSEmbodiment 1. A method of extracting a metal from a sulfide mineral material, the method comprising:(a) contacting the sulfide mineral material with a siderophore under reaction conditions such that the metal contained within the sulfide mineral material is solubilized and released; and(b) collecting the released metal, thereby extracting the metal from the sulfide mineral material. Embodiment 2. The method of embodiment 1, wherein the sulfide mineral material comprises an ore, a rock, a natural sulfide mineral material, a man-made sulfide mineral material, or any combination thereof.Embodiment 3. The method of embodiment 1, wherein the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof.Embodiment 4. The method of any one of the preceding embodiments, wherein the sulfide mineral material comprises chalcopyrite.Embodiment 5. The method of any one of the preceding embodiments, wherein the sulfide mineral material comprises laterite.Embodiment 6. The method of any one of the preceding embodiments, wherein the sulfide mineral material comprises slag.Embodiment 7. The method of any one of the preceding embodiments, wherein the siderophore is derived from an organism selected from the group comprising Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.Attorney Docket No. 66122-710.601Embodiment 8. The method of any one of the preceding embodiments, wherein the siderophore is selected from the group consisting of: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of py overdine, PyoPpC-3B, pyridine-2,6-dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof.Embodiment 9. The method of any one of the preceding embodiments, wherein the siderophore comprises deferoxamine B.Embodiment 10. The method of any one of the preceding embodiments, wherein the siderophore comprises deferoxamine E.Embodiment 11. The method of any one of the preceding embodiments, wherein the siderophore comprises pyoverdine.Embodiment 12. The method of any one of the preceding embodiments, wherein the siderophore comprises pyoverdine or a derivative of pyoverdine.Embodiment 13. The method of any one of the preceding embodiments, wherein the siderophore comprises PyoPpC-3B.Embodiment 14. The method of any one of the preceding embodiments, wherein the siderophore comprises azotochelin.Embodiment 15. The method of any one of the preceding embodiments, wherein the siderophore is purified from an organism prior to the contacting.Embodiment 16. The method of any one of the preceding embodiments, wherein the organism is selected from the group consisting of: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91 , Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus,Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.Attorney Docket No. 66122-710.601Embodiment 17. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a temperature from about 10 °C to about 110 °C.Embodiment 18. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a temperature from about 20 °C to about 35 °C.Embodiment 19. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a pH from about 3 to about 12.Embodiment 20. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a pH from about 5 to about 7.Embodiment 21. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a pH of about 4.Embodiment 22. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a pH of about 6.Embodiment 23. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a weak acid.Embodiment 24. The method of any one of the preceding embodiments, wherein the reaction conditions comprise a weak organic acid.Embodiment 25. The method of any one of the preceding embodiments, wherein the reaction is performed with agitation or without agitation.Embodiment 26. The method of any one of the preceding embodiments, wherein the contacting is for at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 60 hours, or at least about 72 hours.Embodiment 27. The method of any one of the preceding embodiments, wherein the contacting is for at most about at most about 24 hours, at most about 36 hours, at most about 48 hours, at most about 60 hours, or at most about 72 hours.Embodiment 28. The method of any one of the preceding embodiments, wherein the contacting is for about 24 hours, about 36 hours, about 48 hours, about 60 hours, or about 72 hours.Embodiment 29. The method of any one of the preceding embodiments, wherein the siderophore facilitates extraction of a metal from the sulfide mineral material by acidolysis, complexolysis, redoxolysis, or any combination thereof.Embodiment 30. The method of any one of the preceding embodiments, wherein the metal is selected from the group consisting of: lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, gold, silver, molybdenum, selenium, lead, beryllium, tellurium, and any combination thereof.Attorney Docket No. 66122-710.601Embodiment 31. The method of any one of the preceding embodiments, wherein the metal comprises lithium.Embodiment 32. The method of any one of the preceding embodiments, wherein the metal comprises magnesium.Embodiment 33. The method of any one of the preceding embodiments, wherein the metal comprises nickel.Embodiment 34. The method of any one of the preceding embodiments, wherein the metal comprises copper.Embodiment 35. The method of any one of the preceding embodiments, wherein the metal comprises cobalt.Embodiment 36. The method of any one of the preceding embodiments, wherein the metal comprises zinc.Embodiment 37. The method of any one of the preceding embodiments, wherein the metal comprises a rare earth element.Embodiment 38. The method of any one of the preceding embodiments, wherein the metal is released into a solution.Embodiment 39. The method of embodiment 38, further comprising extracting the metal from the solution.Embodiment 40. The method of embodiment 38 or 39, further comprising purifying the metal from the solution, thereby generating a purified metal.Embodiment 41. The method of embodiment 40, wherein the purified metal has a purity of at least about 80%.Embodiment 42. The method of embodiment 40, wherein the purified metal has a purity of at least about 90%.Embodiment 43. The method of embodiment 40, wherein the purified metal has a purity of at least about 95%.Embodiment 44. The method of embodiment 40, wherein the purified metal has a purity of at least about 99%.Embodiment 45. The method of embodiment 40, wherein the purified metal has a purity of at least about 99.99%.Embodiment 46. The method of embodiment 40, wherein the purified metal has a purity of at least about 99.999%.Embodiment 47. The method of any one of embodiments 40 to 46, wherein the purified metal is purified lithium.Attorney Docket No. 66122-710.601Embodiment 48. The method of embodiment 47, wherein the purified lithium is industrial grade, battery grade, or pharmaceutical grade.Embodiment 49. The method of any one of the preceding embodiments, wherein the method is performed in situ or ex situ.Embodiment 50. The method of any one the preceding embodiments, wherein the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5%, or higher. Embodiment 51. The method of any one the preceding embodiments, wherein the method has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher. Embodiment 52. The method of any one the preceding embodiments, wherein the siderophore is produced in a host cell or in a cell-free production system.Embodiment 53. The method of embodiment 52, wherein the host cell comprises a bacterial cell.Embodiment 54. The method of embodiment 53, wherein the bacterial cell is selected from the group consisting of: a Pseudomonas bacteria, Streptomyces bacteria, and a Azotobacter bacteria.Embodiment 55. The method of embodiment 54, wherein the Pseudomonas bacteria is selected from the group consisting of: Pseudomonas putida, Pseudomonas fluorescens, and Pseudomonas azotoformans.Embodiment 56. The method of embodiment 54, wherein the Streptomyces bacteria comprises Streptomyces pilosus.Embodiment 57. The method of embodiment 54, wherein the Azotobacter bacteria comprises Azotobacter vinelandii.Embodiment 58. A reaction mixture comprising a sulfide mineral material and a siderophore.Embodiment 59. The reaction mixture of embodiment 58, wherein the sulfide mineral material and the siderophore are contacted.Embodiment 60. The reaction mixture of embodiment 58 or embodiment 59, wherein the reaction mixture is under reaction conditions.Attorney Docket No. 66122-710.601Embodiment 61. The reaction mixture of embodiment 59 or 60, wherein the contacting results in a metal contained within the sulfide mineral material is solubilized and released. Embodiment 62. The reaction mixture of embodiment 61, wherein the metal is collected. Embodiment 63. The reaction mixture of any one of the preceding embodiments, wherein the sulfide mineral material comprises an ore, a rock, a natural sulfide mineral material, a man-made sulfide mineral material, or any combination thereof.Embodiment 64. The reaction mixture of any one of the preceding embodiments, wherein the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, hauerite, jamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof.Embodiment 65. The reaction mixture of any one of the preceding embodiments, wherein the sulfide mineral material comprises chalcopyrite.Embodiment 66. The reaction mixture of any one of the preceding embodiments, wherein the sulfide mineral material comprises laterite.Embodiment 67. The reaction mixture of any one of the preceding embodiments, wherein the sulfide mineral material comprises slag.Embodiment 68. The reaction mixture of any one of the preceding embodiments, wherein the siderophore is derived from an organism selected from the group comprising Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.Embodiment 69. The reaction mixture of any one of the preceding embodiments, wherein the siderophore is selected from the group consisting of: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative ofAttorney Docket No. 66122-710.601 py overdine, PyoPpC-3B, pyridine-2,6-dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof.Embodiment 70. The reaction mixture of any one of the preceding embodiments, wherein the siderophore comprises deferoxamine B.Embodiment 71. The reaction mixture of any one of the preceding embodiments, wherein the siderophore comprises deferoxamine E.Embodiment 72. The reaction mixture of any one of the preceding embodiments, wherein the siderophore comprises pyoverdine.Embodiment 73. The reaction mixture of any one of the preceding embodiments, wherein the siderophore comprises pyoverdine or a derivative of pyoverdine.Embodiment 74. The reaction mixture of any one of the preceding embodiments, wherein the siderophore comprises PyoPpC-3B.Embodiment 75. The reaction mixture of any one of the preceding embodiments, wherein the siderophore comprises azotochelin.Embodiment 76. The reaction mixture of any one of the preceding embodiments, wherein the siderophore is purified from an organism prior to the contacting.Embodiment 77. The reaction mixture of any one of the preceding embodiments, wherein the organism is selected from the group consisting of: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91 , Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluor escens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus,Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.Embodiment 78. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a temperature from about 10 °C to about 110 °C.Embodiment 79. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a temperature from about 20 °C to about 35 °C.Embodiment 80. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a pH from about 3 to about 12.Attorney Docket No. 66122-710.601Embodiment 81. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a pH from about 5 to about 7.Embodiment 82. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a pH of about 4.Embodiment 83. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a pH of about 6.Embodiment 84. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a weak acid.Embodiment 85. The reaction mixture of any one of the preceding embodiments, wherein the reaction conditions comprise a weak organic acid.Embodiment 86. The reaction mixture of any one of the preceding embodiments, wherein the reaction is performed with agitation or without agitation.Embodiment 87. The reaction mixture of any one of the preceding embodiments, wherein the contacting is for at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 60 hours, or at least about 72 hours.Embodiment 88. The reaction mixture of any one of the preceding embodiments, wherein the contacting is for at most about at most about 24 hours, at most about 36 hours, at most about 48 hours, at most about 60 hours, or at most about 72 hours.Embodiment 89. The reaction mixture of any one of the preceding embodiments, wherein the contacting is for about 24 hours, about 36 hours, about 48 hours, about 60 hours, or about 72 hours.Embodiment 90. The reaction mixture of any one of the preceding embodiments, wherein the siderophore facilitates extraction of a metal from the sulfide mineral material by acidolysis, compl exolysis, redoxolysis, or any combination thereof.Embodiment 91. The reaction mixture of any one of the preceding embodiments, wherein the metal is selected from the group consisting of: lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, gold, silver, molybdenum, selenium, lead, beryllium, tellurium, and any combination thereof.Embodiment 92. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises lithium.Embodiment 93. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises magnesium.Embodiment 94. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises nickel.Attorney Docket No. 66122-710.601Embodiment 95. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises copper.Embodiment 96. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises cobalt.Embodiment 97. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises zinc.Embodiment 98. The reaction mixture of any one of the preceding embodiments, wherein the metal comprises a rare earth element.Embodiment 99. The reaction mixture of any one of the preceding embodiments, wherein the metal is released into a solution.Embodiment 100. The reaction mixture of embodiment 99, further comprising extracting the metal from the solution.Embodiment 101. The reaction mixture of embodiment 99 or 100, further comprising purifying the metal from the solution, thereby generating a purified metal.Embodiment 102. The reaction mixture of embodiment 101, wherein the purified metal has a purity of at least about 80%.Embodiment 103. The reaction mixture of embodiment 101, wherein the purified metal has a purity of at least about 90%.Embodiment 104. The reaction mixture of embodiment 101, wherein the purified metal has a purity of at least about 95%.Embodiment 105. The reaction mixture of embodiment 101, wherein the purified metal has a purity of at least about 99%.Embodiment 106. The reaction mixture of embodiment 101, wherein the purified metal has a purity of at least about 99.99%.Embodiment 107. The reaction mixture of embodiment 101, wherein the purified metal has a purity of at least about 99.999%.Embodiment 108. The reaction mixture of any one of embodiments 101 to 107, wherein the purified metal is purified lithium.Embodiment 109. The reaction mixture of embodiment 108, wherein the purified lithium is industrial grade, battery grade, or pharmaceutical grade.Embodiment 110. The reaction mixture of any one of the preceding embodiments, wherein the reaction mixture is performed in situ or ex situ.Embodiment 111. The reaction mixture of any one the preceding embodiments, wherein the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at leastAttorney Docket No. 66122-710.601 about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5%, or higher.Embodiment 112. The reaction mixture of any one the preceding embodiments, wherein the reaction mixture has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher.Embodiment 113. The reaction mixture of any one the preceding embodiments, wherein the siderophore is produced in a host cell or in a cell-free production system.Embodiment 114. The reaction mixture of embodiment 113, wherein the host cell comprises a bacterial cell.Embodiment 115. The reaction mixture of embodiment 114, wherein the bacterial cell is selected from the group consisting of: a Pseudomonas bacteria, Streptomyces bacteria, and a Azotobacter bacteria.Embodiment 116. The reaction mixture of embodiment 115, wherein the Pseudomonas bacteria is selected from the group consisting of: Pseudomonas putida, Pseudomonas fluorescens, and Pseudomonas azotoformans.Embodiment 117. The reaction mixture of embodiment 115, wherein the Streptomyces bacteria comprises Streptomyces pilosus.Embodiment 118. The reaction mixture of embodiment 115, wherein Azotobacter bacteria comprises Azotobacter vinelandii.

Claims

Attorney Docket No. 66122-710.601CLAIMSWHAT IS CLAIMED IS:

1. A method of extracting a metal from a sulfide mineral material, the method comprising:(a) contacting the sulfide mineral material with a siderophore under reaction conditions such that the metal contained within the sulfide mineral material is solubilized and released; and(b) collecting the released metal, thereby extracting the metal from the sulfide mineral material.

2. The method of claim 1, wherein the sulfide mineral material comprises an ore, a rock, a natural sulfide mineral material, a man-made sulfide mineral material, or any combination thereof.

3. The method of claim 1, wherein the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof.

4. The method of any one of the preceding claims, wherein the sulfide mineral material comprises chalcopyrite.

5. The method of any one of the preceding claims, wherein the sulfide mineral material comprises laterite.

6. The method of any one of the preceding claims, wherein the sulfide mineral material comprises slag.

7. The method of any one of the preceding claims, wherein the siderophore is derived from an organism selected from the group comprising Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae,Attorney Docket No. 66122-710.601Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia peslis. and any combination thereof.

8. The method of any one of the preceding claims, wherein the siderophore is selected from the group consisting of: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, ornibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of pyoverdine, PyoPpC-3B, pyridine-2,6-dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof.

9. The method of any one of the preceding claims, wherein the siderophore comprises deferoxamine B.

10. The method of any one of the preceding claims, wherein the siderophore comprises deferoxamine E.

11. The method of any one of the preceding claims, wherein the siderophore comprises pyoverdine.

12. The method of any one of the preceding claims, wherein the siderophore comprises pyoverdine or a derivative of pyoverdine.

13. The method of any one of the preceding claims, wherein the siderophore comprises PyoPpC-3B.

14. The method of any one of the preceding claims, wherein the siderophore comprises azotochelin.

15. The method of any one of the preceding claims, wherein the siderophore comprises pyochelin.

16. The method of any one of the preceding claims, wherein the siderophore comprises azotobactin.

17. The method of any one of the preceding claims, wherein the siderophore comprises ornibactin.

18. The method of any one of the preceding claims, wherein the siderophore is extracted from an organism prior to the contacting.

19. The method of any one of the preceding claims, wherein the siderophore is purified from an organism prior to the contacting.

20. The method of any one of the preceding claims, wherein the organism is selected from the group consisting of: Acinetobacter baumannii, Azotobacter vinelandii,Attorney Docket No. 66122-710.601Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91 , Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.

21. The method of any one of the preceding claims, wherein the reaction conditions comprise a temperature from about 10 °C to about 110 °C.

22. The method of any one of the preceding claims, wherein the reaction conditions comprise a temperature from about 20 °C to about 35 °C.

23. The method of any one of the preceding claims, wherein the reaction conditions comprise a pH from about 3 to about 12.

24. The method of any one of the preceding claims, wherein the reaction conditions comprise a pH from about 5 to about 7.

25. The method of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 4.

26. The method of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 6.

27. The method of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 7 to about 9.

28. The method of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 9.

29. The method of any one of the preceding claims, wherein the reaction conditions comprise a weak acid.

30. The method of any one of the preceding claims, wherein the reaction conditions comprise a weak organic acid.

31. The method of any one of the preceding claims, wherein the reaction conditions comprise a buffer.

32. The method of any one of the preceding claims, wherein the reaction conditions comprise an inorganic buffer.Attorney Docket No. 66122-710.60133. The method of any one of the preceding claims, wherein the reaction conditions comprise an organic buffer.

34. The method of any one of the preceding claims, wherein the reaction conditions comprise a citrate buffer.

35. The method of any one of the preceding claims, wherein the sulfide mineral material is treated with an oxidizing agent prior to the contacting the sulfide mineral material with the siderophore, and wherein the oxidizing agent is used as a catalyst.

36. The method of any one of the preceding claims, wherein the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent is used as a catalyst.

37. The method of claim 35 or 36, wherein the oxidizing agent comprises pyocyanin, hydrogen peroxide, or sodium hypochlorite.

38. The method of any one of claims 35 to 37, wherein the oxidizing agent comprises pyocyanin.

39. The method of any one of the preceding claims, wherein the reaction conditions comprise an inorganic salt.

40. The method of claim 39, wherein the inorganic salt comprises sodium chloride.

41. The method of any one of the preceding claims, wherein the reaction is performed with agitation or without agitation.

42. The method of any one of the preceding claims, wherein the contacting is for at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 60 hours, at least about 72 hours, at least about 84 hours, at least about 96 hours, at least about 108 hours, or at least about 120 hours.

43. The method of any one of the preceding claims, wherein the contacting is for at most about at most about 24 hours, at most about 36 hours, at most about 48 hours, at most about 60 hours, at most about 72 hours, at most about 84 hours, at most about 96 hours, at most about 108 hours, or at most about 120 hours.

44. The method of any one of the preceding claims, wherein the contacting is for about 24 hours, about 36 hours, about 48 hours, about 60 hours, about 72 hours, about 84 hours, about 96 hours, about 108 hours, or about 120 hours.

45. The method of any one of the preceding claims, wherein the siderophore facilitates extraction of a metal from the sulfide mineral material by acidolysis, complexolysis, redoxolysis, or any combination thereof.

46. The method of any one of the preceding claims, wherein the metal is selected from the group consisting of: lithium, aluminum, iron, nickel, cobalt, copper, manganese,Attorney Docket No. 66122-710.601 magnesium, zinc, a rare earth element, gold, silver, molybdenum, selenium, lead, beryllium, tellurium, and any combination thereof.

47. The method of any one of the preceding claims, wherein the metal comprises lithium.

48. The method of any one of the preceding claims, wherein the metal comprises magnesium.

49. The method of any one of the preceding claims, wherein the metal comprises nickel.

50. The method of any one of the preceding claims, wherein the metal comprises copper.

51. The method of any one of the preceding claims, wherein the metal comprises cobalt.

52. The method of any one of the preceding claims, wherein the metal comprises zinc.

53. The method of any one of the preceding claims, wherein the metal comprises a rare earth element.

54. The method of any one of the preceding claims, wherein the metal is released into a solution.

55. The method of claim 54, further comprising extracting the metal from the solution.

56. The method of claim 54 or 55, further comprising purifying the metal from the solution, thereby generating a purified metal.

57. The method of claim 56, wherein the purified metal has a purity of at least about 80%.

58. The method of claim 56, wherein the purified metal has a purity of at least about 90%.

59. The method of claim 56, wherein the purified metal has a purity of at least about 95%.

60. The method of claim 56, wherein the purified metal has a purity of at least about 99%.

61. The method of claim 56, wherein the purified metal has a purity of at least about99.99%.

62. The method of claim 56, wherein the purified metal has a purity of at least about 99.999%.

63. The method of any one of claims 56 to 62, wherein the purified metal is purified lithium.

64. The method of claim 63, wherein the purified lithium is industrial grade, battery grade, or pharmaceutical grade.

65. The method of any one of the preceding claims, wherein the method is performed in situ or ex situ.

66. The method of any one the preceding claims, wherein the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5%, or higher.Attorney Docket No. 66122-710.60167. The method of any one the preceding claims, wherein the method has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher.

68. The method of any one the preceding claims, wherein the method is performed in batches.

69. The method of any one the preceding claims, wherein the method is performed continuously.

70. The method of any one the preceding claims, wherein the siderophore is produced in a host cell or in a cell-free production system.

71. The method of claim 69, wherein the host cell comprises a bacterial cell.

72. The method of claim 70, wherein the bacterial cell is selected from the group consisting of: a Pseudomonas bacteria, Streptomyces bacteria, and a Azotobacter bacteria.

73. The method of claim 71, wherein the Pseudomonas bacteria is selected from the group consisting of: Pseudomonas putida, Pseudomonas fluorescens, and Pseudomonas azotoformans.

74. The method of claim 71, wherein the Streptomyces bacteria comprises Streptomyces pilosus.

75. The method of claim 71, wherein the Azotobacter bacteria comprises Azotobacter vinelandii.

76. A reaction mixture comprising a sulfide mineral material and a siderophore.

77. The reaction mixture of claim 76, wherein the sulfide mineral material and the siderophore are contacted.

78. The reaction mixture of claim 76 or claim 77, wherein the reaction mixture is under reaction conditions.

79. The reaction mixture of claim 77 or 78, wherein the contacting results in a metal contained within the sulfide mineral material is solubilized and released.

80. The reaction mixture of claim 79, wherein the metal is collected.

81. The reaction mixture of any one of the preceding claims, wherein the sulfide mineral material comprises an ore, a rock, a natural sulfide mineral material, a man-made sulfide mineral material, or any combination thereof.Attorney Docket No. 66122-710.60182. The reaction mixture of any one of the preceding claims, wherein the sulfide mineral material comprises acanthite, arsenopyrite, bournonite, bornite, chalcocite, chalcopyrite, cinnabar, cobaltite, covellite, cylindrite, enargite, galena, gersdorffite, haueritejamesonite, laterite, marcasite, millerite, molybdenite, orpiment, pentlandite, proustite, pyrite, pyrrhotite, pyrargyrite, realgar, sphalerite, stibnite, tennantite, tetrahedrite, tungstenite, slag, or any combination thereof.

83. The reaction mixture of any one of the preceding claims, wherein the sulfide mineral material comprises chalcopyrite.

84. The reaction mixture of any one of the preceding claims, wherein the sulfide mineral material comprises laterite.

85. The reaction mixture of any one of the preceding claims, wherein the sulfide mineral material comprises slag.

86. The reaction mixture of any one of the preceding claims, wherein the siderophore is derived from an organism selected from the group comprising Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli,Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.

87. The reaction mixture of any one of the preceding claims, wherein the siderophore is selected from the group consisting of: aerobactin, agrobactin, aminochelin, azotobactin, azotochelin, bacillibactin, deferoxamine B, deferoxamine E, desferrioxamine B, desferrioxamine E, enterobactin, ferrichrome, fusarinine C, micacocidin, mycobactin, omibactin, protochelin, pseudobactin, pyochelin, pyoverdine, pyoverdine or a derivative of pyoverdine, PyoPpC-3B, pyridine-2,6- dithiocarboxylate, rhizobactin 1021, rhodotorulic acid, salmochelin, schizokinen, vibrioferrin, vibriobactin, vicibactin, yersiniabactin, and any combination thereof.

88. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises deferoxamine B.Attorney Docket No. 66122-710.60189. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises deferoxamine E.

90. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises py overdine.

91. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises py overdine or a derivative of py overdine.

92. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises PyoPpC-3B.

93. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises azotochelin.

94. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises pyochelin.

95. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises azotobactin.

96. The reaction mixture of any one of the preceding claims, wherein the siderophore comprises ornibactin.

97. The reaction mixture of any one of the preceding claims, wherein the siderophore is derived from an organism prior to the contacting.

98. The reaction mixture of any one of the preceding claims, wherein the siderophore is purified from an organism prior to the contacting.

99. The reaction mixture of any one of the preceding claims, wherein the organism is selected from the group consisting of: Acinetobacter baumannii, Azotobacter vinelandii, Bacillus anthracis, Bacillus megaterium, Bacillus subtilis, Bacillus thuringiensis, Burkholderia cepacia, Escherichia coli, Fusarium roseum, Klebsiella pneumonia, Mycobacterium smegmatis, Mycobacterium tuberculosis, Pantoea eucalypti M91, Pantoea vagans C9-1, Pseudomonas aeruginosa, Pseudomonas azotoformans, Pseudomonas BIO, Pseudomonas fluorescens, Pseudomonas putida, Pseudomonas sp., Pseudomonas syringae, Rhizobium leguminosarum, Rhizobium meliloti, Rhizobium radiobacter, Rhodotorula pilimanae, Streptomyces coelicolor, Streptomyces pilosus, Streptomyces coelicolor, Ustilago sphaerogena, Vibrio cholerae, Yersinia pestis, and any combination thereof.

100. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a temperature from about 10 °C to about 110 °C.Attorney Docket No. 66122-710.601101. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a temperature from about 20 °C to about 35 °C.

102. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a pH from about 3 to about 12.

103. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a pH from about 5 to about 7.

104. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 4.

105. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 6.

106. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 8 to about 9.

107. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a pH of about 9.

108. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a weak acid.

109. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a weak organic acid.

110. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a buffer.

111. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise an inorganic buffer.

112. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise an organic buffer.

113. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise a citrate buffer.

114. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise an oxidizing agent, wherein the oxidizing agent is used as a catalyst.

115. The reaction mixture of claim 114, wherein the oxidizing agent comprises pyocyanin, hydrogen peroxide, or sodium hypochlorite.

116. The reaction mixture of claim 114 or claim 115, wherein the oxidizing agent comprises pyocyanin.Attorney Docket No. 66122-710.601117. The reaction mixture of any one of the preceding claims, wherein the reaction conditions comprise an inorganic salt.

118. The reaction mixture of claim 117, wherein the inorganic salt comprises sodium chloride.

119. The reaction mixture of any one of the preceding claims, wherein the reaction is performed with agitation or without agitation.

120. The reaction mixture of any one of the preceding claims, wherein the contacting is for at least about 24 hours, at least about 36 hours, at least about 48 hours, at least about 60 hours, at least about 72 hours, at least about 84 hours, at least about 96 hours, at least about 108 hours, or at least about 120 hours.

121. The reaction mixture of any one of the preceding claims, wherein the contacting is for at most about at most about 24 hours, at most about 36 hours, at most about 48 hours, at most about 60 hours, at most about 72 hours, at most about 84 hours, at most about 96 hours, at most about 108 hours, or at most about 120 hours.

122. The reaction mixture of any one of the preceding claims, wherein the contacting is for about 24 hours, about 36 hours, about 48 hours, about 60 hours, about 72 hours, about 84 hours, about 96 hours, about 108 hours, or about 120 hours.

123. The reaction mixture of any one of the preceding claims, wherein the siderophore facilitates extraction of a metal from the sulfide mineral material by acidolysis, compl exolysis, redoxolysis, or any combination thereof.

124. The reaction mixture of any one of the preceding claims, wherein the metal is selected from the group consisting of: lithium, aluminum, iron, nickel, cobalt, copper, manganese, magnesium, zinc, a rare earth element, gold, silver, molybdenum, selenium, lead, beryllium, tellurium, and any combination thereof.

125. The reaction mixture of any one of the preceding claims, wherein the metal comprises lithium.

126. The reaction mixture of any one of the preceding claims, wherein the metal comprises magnesium.

127. The reaction mixture of any one of the preceding claims, wherein the metal comprises nickel.

128. The reaction mixture of any one of the preceding claims, wherein the metal comprises copper.

129. The reaction mixture of any one of the preceding claims, wherein the metal comprises cobalt.Attorney Docket No. 66122-710.601130. The reaction mixture of any one of the preceding claims, wherein the metal comprises zinc.

131. The reaction mixture of any one of the preceding claims, wherein the metal comprises a rare earth element.

132. The reaction mixture of any one of the preceding claims, wherein the metal is released into a solution.

133. The reaction mixture of claim 132, further comprising extracting the metal from the solution.

134. The reaction mixture of claim 132 or 133, further comprising purifying the metal from the solution, thereby generating a purified metal.

135. The reaction mixture of claim 134, wherein the purified metal has a purity of at least about 80%.

136. The reaction mixture of claim 134, wherein the purified metal has a purity of at least about 90%.

137. The reaction mixture of claim 134, wherein the purified metal has a purity of at least about 95%.

138. The reaction mixture of claim 134, wherein the purified metal has a purity of at least about 99%.

139. The reaction mixture of claim 134, wherein the purified metal has a purity of at least about 99.99%.

140. The reaction mixture of claim 134, wherein the purified metal has a purity of at least about 99.999%.

141. The reaction mixture of any one of claims 134 to 140, wherein the purified metal is purified lithium.

142. The reaction mixture of claim 141, wherein the purified lithium is industrial grade, battery grade, or pharmaceutical grade.

143. The reaction mixture of any one of the preceding claims, wherein the reaction mixture is performed in situ or ex situ.

144. The reaction mixture of any one the preceding claims, wherein the siderophore has an extraction efficiency of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5%, or higher.Attorney Docket No. 66122-710.601145. The reaction mixture of any one the preceding claims, wherein the reaction mixture has a maximum metal extraction rate of at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 98% at least about 99%, at least about 99.5% or higher.

146. The reaction mixture of any one the preceding claims, wherein the siderophore is produced in a host cell or in a cell-free production system.

147. The reaction mixture of claim 146, wherein the host cell comprises a bacterial cell.

148. The reaction mixture of claim 147, wherein the bacterial cell is selected from the group consisting of: a Pseudomonas bacteria, Streptomyces bacteria, and a Azotobacter bacteria.

149. The reaction mixture of claim 148, wherein the Pseudomonas bacteria is selected from the group consisting of: Pseudomonas putida, Pseudomonas fluorescens, and Pseudomonas azotoformans .

150. The reaction mixture of claim 148, wherein the Streptomyces bacteria comprises Streptomyces pilosus.

151. The reaction mixture of claim 148, wherein the Azotobacter bacteria comprises Azotobacter vinelandii.

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