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By R. S. Busk, E. G. Bobalek

THE relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.1,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittlement of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.3 To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Recently it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate microporosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.1 Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H2, solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice .2 For true equilibrium values of solubility, therefore, the pressure at the metal surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1946

By Bruce W. Downing

MagPower has developed methods to control the detrimental formation of hydrogen that occurs in electrochemical reactions in numerous commercial applications such as the Magnesium-Air Fuel Cell, electrowinning, zinc alkaline batteries, hydrogen embrittlement, waste water/ metal recycling and coolants. The company?s approach to an alternative energy source is the development of an environmentally friendly non-toxic alternative power source that generates electricity through a combination of magnesium, oxygen and a saltwater electrolyte with MagPower?s patent pending hydrogen inhibitors. The magnesium-air technology has never reached the commercial stage due to its limiting power output caused by hydrogen generation. MagPowerhas solved this problem and has patents pending on its intellectual property; the Hydrogen Inhibitors and has developed several consumer power units for a variety of applications through licensing agreements. The company has also shown that the inhibitors have an impact on zinc electrowinning through laboratory test work where current efficiency was improved. This will significantly reduce power consumption and increase the efficiency of the electrowinning process, as well as reduce the potential acid mist hazards associated with electrowinning.

Jan 1, 2003

By Akihide Nagao

The behavior of impurity hydrogen that is contained in starting material or picked up during processing has been little investigated up to now. The hydrogen microprint technique is applied to determine the microscopic location of impurity hydrogen during deformation in aluminum without hydrogen charging. Three kinds of pure aluminum of 99.99% are prepared, in which hydrogen content is varied by changing the atmosphere when they are melted and heat-treated. After rolling, tensile specimens with a gage size of 4 x 4 rnm and 0.5 mm in thickness are stamped out from these three kinds of aluminum sheets. These specimens are covered with a liquid nuclear emulsion of silver bromide crystals, stretched by 5,10 and 15 percent plastic strain or fractured, developed and fixed. SEM micrographs reveal a number of silver particles on the slip lines and on the grain boundaries. Also shown is that the more hydrogen present in the specimen, the more silver grains appear on the slip limes and on the grain boundaries. Consequently, it is concluded that impurity hydrogen is transported to the surface with gliding dislocations during deformation.

Jan 1, 1998

By W. McCombe, G. Remple, L. Zunti, M. Bernardin, L. Nightingale-Mercer

"The McClean Lake Mill is located approximately 700 kilometres north of Saskatoon, Saskatchewan, Canada and is operated by AREVA Resources Canada Inc. (AREVA). The mill was designed to process high grade uranium ores, and has been undergoing a multiyear expansion to increase its production capacity to 24 Mlbs U3O8 per annum, while also undergoing upgrades to allow it to safely transition to processing high grade ores from the Cigar Lake Mine. During the metallurgical test work on the Cigar Lake ores, it was identified that some ore zones in the Cigar Lake deposit have a propensity to generate hydrogen gas during acid leaching. Hydrogen is a volatile and explosive gas, which poses obvious safety concerns in the leaching circuit. Uranium processing is further complicated by the fact that an oxidant in the form of oxygen gas or hydrogen peroxide is required to regenerate iron in the leach, which further increases the risk from hydrogen gas. During 2013 Hatch and AREVA designed and engineered a number of novel upgrades for the leaching circuit to mitigate the risk of hydrogen gas evolution in the process. Best in class technology was utilized in addition to control and operating strategy changes to ensure the leaching circuit can be safely operated with ores that can evolve hydrogen gas. This paper reviews the design concepts and modifications implemented on this unique and challenging project.INTRODUCTION The McClean Lake mill was originally designed to process high grade uranium ores, however until 2014 the average ore grade processed was 1%. The facility has been undergoing a multiyear upgrade and expansion to increase its production capacity from 12 to 24 Mlbs U3O8 per annum, while also undergoing upgrades to allow it to safely transition to new high grade ores, averaging 18% U, from the Cigar Lake Mine. During the last round of metallurgical test work on the Cigar Lake ores, it was identified that some ore zones in the Cigar Lake deposit had a higher propensity to generate hydrogen gas during acid leaching than previous test work had indicated. Hydrogen gas is a volatile and explosive gas, which poses obvious safety concerns in the leaching circuit."

Jan 1, 2017

By W. McCombe, G. Remple, L. Nightingale-Mercer

The McClean Lake Mill is located approximately 850 kilometres north of Saskatoon, Saskatchewan, Canada, and is operated by Orano Canada Inc. (Orano). The mill was designed to process high grade uranium ores, and a multi-year expansion was completed in 2014 to increase its production capacity to 24 Mlbs U3O8 per annum. The mill also underwent various upgrades to allow it to safely transition from processing low grade ores to high grade ores from the nearby Cigar Lake Mine. During the metallurgical test work on the Cigar Lake ores, it was identified that some ore zones of the deposit have a propensity to generate hydrogen gas during acid leaching. Hydrogen is a volatile and explosive gas, which poses obvious safety concerns in the leaching circuit. Uranium processing is further complicated by the fact that an oxidant in the form of oxygen gas or hydrogen peroxide is required to regenerate iron in the leach, which further increases the risk posed by hydrogen gas. During 2013 Orano and its consultant Hatch designed and engineered several novel upgrades to the leaching circuit to mitigate the risk of hydrogen gas evolution in the process. Best in class technology was utilized in addition to control and operating strategy changes to ensure the leaching circuit could be safely operated with ores that evolve hydrogen gas. This paper reviews the design concepts and modifications implemented on this unique and challenging project, and also provides an update on the operational reality of hydrogen in the circuit gained through five years of operational experience with hydrogen evolving ores.

Jan 1, 2020

By D. Scott Scovira, Thomas Gustavsson

Exiting WW2, the potential of nitrates and hydrogen peroxide for application as industrial explosives both became known. The technology stream advanced the development and uptake of nitrate-based explosives to the point that they are the current global standard for blasting. Recently environmental issues are influencing the strategic agenda of extractive industries. The mid-2010s saw renewed interest in hydrogen peroxide explosives to eliminate NOx fume. Carbon reduction initiatives in the 2020s provided additional impetus to investigate hydrogen peroxide-based explosives. Hypex Bio is at the forefront of developing and delivering bulk gas sensitized Hydrogen Peroxide Emulsion (HPE) for blasting. HPE consists of hydrogen peroxide along with smaller amounts of fuel and emulsifier. The consistency of HPE is similar to industry- standard nitrate-based emulsions. It is compatible with existing priming and initiation systems. HPE does not contain nitrates and thereby does not produce post blast nitrous oxide fumes nor discharge of nitrates or ammonia to mine water. Importantly, HPE contributes to reduction in total carbon emissions as compared to nitrate-based explosives.

Feb 1, 2025

By Johan Hillman, D. Scott Scovira, Thomas Gustavsson, Alexander Bihlar

Hydrogen Peroxide Emulsion (HPE) explosives are an alternative to conventional commercial explosives. HPE does not contain nitrates or ammonia thus eliminating post-detonation NOx fumes and aqueous nitrate discharge. Production of HPE is less carbon intensive than industry standard ammonium nitrate-based emulsions (ANE) and employment aligns with end users seeking to meet Scope 3 ESG emission targets. Swedish tunneling contractor Implenia Sverige was awarded the Högdalen Depot Expansion Project by the City of Stockholm. Implenia Sverige partnered with Hypex Bio to be the first to pilot the application of a nitrate-free explosive system in a large-scale civil construction tunnel. The purpose of the joint project was to evaluate the operational suitability of replacing conventional nitrate-based bulk explosives with HPE in a large-scale tunnelling project. When the project commenced in September 2023 both standard nitrate-based emulsions and HPE emulsion were used in parallel (Tunnel Right and Tunnel Left) to enable operational, performance, and environmental comparison. Identical drill patterns and initiation techniques were applied to both tunnel headings. Performance data collected included round advance, usage, and perimeter quality. Implenia managed all drilling and charging operations and Hypex Bio provided technical support, including technicians and chemists. HPE is viscous and pumpable using conventional emulsion pumping delivery systems. Variable density functionality enabled loading different charge weights into cut, lifter, production, and perimeter holes. The primary rock type was hard sedimentary gneiss with approximately 150 MPa [21,755 psi] Uniaxial Compressive Strength (UCS). Fracture systems with infilling occurred in both tunnel directions. Rock quality factor was “Good to Very Good” on the RMRb (Rock Mass Rating) scale. Epiroc Boomer rigs were used to drill rounds averaging 4.9 m [16 ft] deep with high accuracy and precise reference positioning.

Jan 26, 2026

By D. Scott Scovira, Thomas Gustavsson

The potential of hydrogen peroxide explosives was introduced to Thomas Gustavsson and Robert Håkland by Dr Miguel Araos through his development of hydrogen peroxide gel compositions (HPG). In 2020, Thomas and Robert developed a concept project with Boliden Minerals and received Swedish government funding to evaluate HPG technology in a mine environment. The project showed HPG reacted violently with mine mineralization and concluded that HPGs did not offer a commercial solution due to safety concerns. Thomas and Robert engaged with Stefan Nilsson to develop hydrogen peroxide emulsion (HPE) compositions and the process techniques to manufacture them. In 2021, laboratory work produced a promising low carbon intensity, nitrate free, ammonia free, emulsion formulation based on industrial grade hydrogen peroxide and a fuel-emulsifier phase. Design and construction of an HPE pilot plant and underground charging unit commenced. The manufacture of hydrogen peroxide emulsion shares several similarities with the production of nitrate-based emulsions in that the plant is a facility to blend a strong oxidizer solution with a liquid fuel phase into a finished emulsion. A key differentiator between HPE and nitrate-based emulsion is that the manufacture of HPE is a cold production technology in that neither the oxidizer phase (HP) nor the fuel-emulsifier phase requires high temperature heating to prepare raw materials. A successful proof-of-concept HPE evaluation ran from April 2022 to October 2022 at Boliden’s Kankberg underground mine in Sweden. This evaluation demonstrated HPE technology's safety, performance, production, handling, and indicative environmental benefits.

Jan 21, 2025

By L. McFarlane, D. Rollwagen

"Madawaska Mines produces a uranium precipitate (83-85% u3o8) using a magnesium oxide slurry to precipitate the uranium from solution. The solution, at approximately 9""0 g/l u3o8 is neutralized to a pH of 7.0. At the Eldorado Nuclear Refinery in Port Hope, the precipitate is not acceptable as a single feed to the refinery process. It was discovered that a 2% silica impurity caused emulsion problems in the solvent extraction column.After extensive studies of possible solutions, such as two-stage precipitation and solvent extraction, an acceptable solution was found. The selective precipitation of uranium at a pH of 3.5-4.0 using Hydrogen Peroxide produces an almost silica free product of higher purity (90-93% u3o8) to that of straight magnesium oxide precipitation. Introduction Madawaska Mines Limited is located four miles southwest of Bancroft, Ontario. The annual production of u3o8 is approximately 610,000 pounds. To produce the final product or yellowcake, nine separate steps are required. These are (1) grinding, (2) dewatering, (3) leaching, (4) acid filtration, (5) clarification, (6) ion exchange, (7) precipitation, (8) washing, and (9) drying and packaging. To illustrate these steps, a complete flowsheet of the mill is displayed on page three.The yellowcake is sent to Eldorado Nuclear Limited in Port Hope, Ontario for further concentrating and refining. As part of their routine specification check, a test called the amenability test is performed. This test indicates how a particular dissolved yellowcake product reacts to solvent extraction. The Madawaska yellowcake did not pass the test."

Jan 1, 1982

By Frank E. Caropreso, William P. Badger

A hydrogen peroxide precipitate process has been adopted by Atlas Minerals for the recovery of uranium oxides from sodium chloride strip solutions. Adoption of the process was based on laboratory and plant tests comparing hydrogen peroxide with other precipitants. Plant operation has demonstrated that the hydrogen peroxide process consistently yields uranium concentrates of high purity and barrens of low uranium content. Increased U3O8 concentration in the product, reduced levels of impurities which incur penalties, and higher product density have produced economic advantages.

Jan 1, 1974

By M I. Pownceby, M A. Rhamdhani, S Palanisamy, D Fellicia, B Satritama, G A. Brooks, A Ang

Metal production have long been using carbon sources as both reducing agents and energy sources. Consequently, the global extractive metal sector contributes significantly to greenhouse gas emissions, accounting for approximately 9.5 per cent. Hydrogen gas offers as a promising ecofriendly alternative to carbon in metallurgical processes, serving as both a reductant and energy supplier with a by-product being only water vapour. However, the implementation of molecular hydrogen faces certain challenges related to the thermodynamics and kinetics of metal oxide reduction. In addressing these challenges, researchers have explored the application of hydrogen plasma, generated by subjecting molecular hydrogen to high energy to produce atomic, ionic and excited hydrogen species. Hydrogen plasma offers thermodynamic and kinetic advantages over molecular hydrogen and carbon-based reductants, exhibiting lower standard Gibbs free energy of reaction and activation energy. Therefore, hydrogen plasma can produce metal in fewer steps, process any oxide feed and feed size and even be used to refine metals. Despite these advantages, challenges exist in utilising hydrogen plasma in extractive metallurgy, including electricity costs, potential reverse reactions and industrial-scale implementation. This study provides a mini review of prior research on hydrogen plasma for metal oxides reduction, particularly iron oxide, as well as state-of-the-art techniques for its use in extractive metallurgy applications by mentioning several reactor types. Future prospects and scale-up possibilities of the hydrogen plasma in extractive metallurgy will also be presented.

Aug 21, 2024

By Juan Ruiz-Ornelas, Yousef Mohassab, Ricardo Morales-Estrella, Hong Yong Sohn, Noemi Ortiz-Lara

The effect of mechanical activation on the reduction kinetics of magnetite concentrate by hydrogen was studied. The magnetite concentrate was milled for 8 h using a planetary mill. After the milling process, the average particle size was reduced from 14 to 4.4 m resulting in a lattice microstrain of 0.30. Thermogravimetric experiments were conducted to focus on the chemical reaction as the rate controlling factor by eliminating external mass transfer effects and using a thin layer of particles to remove interstitial diffusion resistance. The onset temperature of reduction was decreased due to the mechanical activation, and the degree of conversion was decreased by sintering of particles which was confirmed by SEM analyses. In view of the results, a reaction rate expression is discussed from which the activation energy is calculated.

Jan 1, 2016

By B J. Monaghan, R J. Longbottom, S Prabowo, D Del Puerto, B Maisuria, C W. Bumby

The use of hydrogen as a reducing agent can substantially reduce carbon dioxide (CO2) emissions from the ironmaking process. Iron ore fines can be reduced in a fluidised bed (FB) using hydrogen (H2) at high temperatures (>800°C), although several studies have reported the sticking of particles which causes the bed to defluidise, effectively shutting down the process. Here, we report results from the reduction of New Zealand (NZ) titanomagnetite (TTM) ironsands in a small-scale laboratory FB (100 g) at temperatures between 800–1000°C using H2 flow rates up to 5 standard L/min. No sticking phenomena are observed under any of these conditions, which is attributed to the formation of a stable titanium-bearing oxide layer on each particle’s exterior, preventing iron-iron contact at the particle surfaces. Pre-oxidised NZ TTM ironsands have also been studied and shown not to stick. Interestingly, at lower reaction temperatures the reduction kinetics for pre-oxidised ironsands is faster than for as-received ironsands. This increased kinetic rate can be attributed to the preoxidation stage inducing micro-fractures that create a void for the hydrogen to diffuse into the inner regions of the particle. In addition, oxidation of TTM appears to segregate the particle into two distinct phases, a high Aluminium-Magnesium (Al-Mg) phase and a high Titanium (Ti) phase. The findings are important as increasing the operating temperature of the FB reactor results in a faster reaction rate and higher gas utilisation, making the process more economically attractive. Furthermore, oxidation of NZ TTM ironsands results in a faster reduction rate at lower temperatures (800°C– 900°C) opening the opportunity to reduce the reaction temperature which might be beneficial in a final commercial-scale process.

Sep 18, 2023

By S Hapugoda, Y Tang, L Lu

The steel industry is one of the global leading CO2 emitters, accounting for approximately 7 per cent of global anthropogenic CO2 emissions. In 2022, the world produced 1878.5 Mt of crude steel. About 70.8 per cent of the world’s crude steel was produced by integrated steel mills through the blast furnace and basic oxygen furnace (BF-BOF) process, while the remainder was produced largely by mini mills using electrical arc furnaces (EAF). Compared with gas-based DRI and scrap-based EAF processes, the direct CO2 emissions from the BF-BOF process and the coal based DRI and EAF process are significantly more, as both the processes rely heavily on fossil fuels, such as coke and pulverised coal, to provide energy and reduce iron oxides. Hydrogen is very reactive and reduces iron oxides to metallic iron without generating CO2. Therefore, substitution of hydrogen for fossil fuels in these processes presents a good opportunity to significantly decarbonise the steel industry. This paper will first discuss the thermodynamic and kinetic characteristics of hydrogen and carbothermic reductions of iron oxides and then examine the behaviours of different ore types present in Australia iron ores during hydrogen reduction.

Sep 18, 2023

By Liu Zhonghua

Hydrogen reduction of cobalt sulfide (Co9S8) was experimentally investigated in the temperature range 813-1053 K. The results revealed that the reaction kinetics can be described by the shrinking core mod¬el in chemical control regime at low temperatures, it is of first order with respect to hydrogen concentration, and the reaction activation energy is 67.4 kJ/mol. The SEM second electron images of the samples before and after experiments showed that the swelling of the sample above 973 K is due to the formation of metallic cobalt whiskers.

Jan 1, 1992

By B. D. Pandey, D. Bagchi, Premchand

During the separation and recovery of metals from the ammoniacal leach liquor of Indian Ocean nodules by solvent extraction-electrowinning (SX-EW) in close-loop operation, the copper electrolyte containing ~40g/L Cu, 20 g/L Ni and 180 g/L sulphuric acid is bled-off to control the impurities. The recovery of copper and nickel as powders has been examined from the copper bleed solution following partial decopperisation, crystallization of mixed sulphate of the two metals and aqueous hydrogen reduction. From the dissolved sulphate solution containing 17.68 g/L Cu, 18.83 g/L Ni and 0.03 g/L Fe, the copper powder was precipitated at initial hydrogen pressure of 26 bar in an autoclave in 90 min at 140 °C. The residual copper from the spent solution was removed as sulphide and nickel powder was then recovered (99%) in two stages from a solution of pH 4.5 at 40 bar pressure and 190 °C. However, 98% nickel recovery in one stage was achieved when hydrogen reduction was carried out from an ammoniacal solution in the pH range 9-11. Copper and nickel powders were produced from the bleed solution with acceptable purity and specifications suitable for P/M applications.

Jan 1, 2004

By Hämäläinen M., O. Hyvärinen, E. Jääskeläinen

HydroCopperTM is a new hydrometallurgical process for the treatment of copper sulphide concentrates, which has been developed by Outokumpu. The process includes chloride leaching of copper concentrate, solution purification and precipitation of copper(I) oxide, an intermediate product, which is reduced and cast into copper products. The reduction can be carried out by pyrometallurgical methods or hydrometallurgically in an autoclave. This paper discusses the thermodynamic and kinetic aspects of the hydrogen reduction of copper(I) oxide in an autoclave. The results of the laboratory tests are presented and discussed. Finally, the autoclave method is compared with other options.

Jan 1, 2004

By K. Osseo-Asare

Rate laws for the hydrogen reduction of metal ions are typically of the form: [r = -d[M(II)]/dt = k[M(II)]xPy2H] where k is an apparent rate constant, [M(II)] and PH2 represent dissolved metal concentration and hydrogen pressure respectively, while x = 0 - 1 and y = 0.5 - 2. Half-order dependences have been reported for some M(II)/H2 systems; however, no satisfactory explanations have been offered. In an effort to bridge this gap in our understanding, the published precipitation rate data (for M(II) = Cu(II), Ni(II), and Co(II)) are reviewed (with emphasis on the reported reaction orders) and compared with the corresponding but limited electrochemical polarization data. Based on the available literature on the electrochemical kinetics of the M/M(II) and H2/H+ systems it is demonstrated theoretically that, under certain conditions (e.g., in the presence of electron-conducting solids), the rate of the M(II)/H2 reaction can be expressed as: [-d[M2+]/dt = k[M2+]2/1P2/12H] It is concluded that electrochemical processes probably play an important role in the hydrogen reduction of metal ions, especially for systems that involve heterogeneous catalysis.

Jan 1, 2003

By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By N. Fukatsu

The recent development of galvanic cell-type hydrogen sensor for molten copper was outlined. The principle of the sensing mechanism, the fundamental structure of the sensor, and its performance as a process control device are discussed based on experimental work undertaken by the authors. Besides sensors based on usual perovskite-type proton conducting oxide, those using magnesium-doped alpha alumina, which was recently known as a proton conductor, were investigated and the results at the laboratory scale are reported. Considering the excellent sensitivity at high temperature and the stability to the disturbance from the attendant oxygen activity, magnesium-doped alpha alumina was regarded to be a superior material for the sensors used for such purposes.

Jan 1, 2007