Mark Foreman

Mark Foreman
Chalmers University of Technology · Department of Chemical and Biological Engineering

Docent

About

154
Publications
54,696
Reads
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4,702
Citations
Citations since 2017
26 Research Items
1482 Citations
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2017201820192020202120222023050100150200250
2017201820192020202120222023050100150200250
Introduction
I am an inorganic / organic chemist many of whose interests relate to recycling / nuclear / radioactive matters. However I do have some interests which are nothing to do with the above three. I worked on the ColaBats project on the recycling of cobalt and lanthanides from used electrical cells using ionic liquids. This resulted in my developing an interest in activity coefficents in deep eutetic solvents and ionic liquids. I do solvent extraction using at least one of these types of liquids as a layer. These solvent extraction experiments are done to obtain a better understanding of activity coefficents and the solvents. I have been working on the fission product chemistry which is associated with serious nuclear accidents. Much of this has been organic iodine chemistry.
Additional affiliations
July 2007 - present
Chalmers University of Technology
Position
  • Professor (Associate)
October 2001 - December 2006
University of Reading
Position
  • Research Associate
Description
  • Working on INORGPORE, PARTNEW and EUROPART in Mike Hudson's group. Most of this work was on new extraction agents for use in the solvent extraction of trivalent post-plutonium metals from mixtures in nitric acid which also contained lanthanides.
September 2000 - August 2001
Imperial College London
Position
  • Research Associate
Description
  • Organometallics, chemistry of the Tm and Bm ligands with Mo, W, Ru, Rh and Os
Education
October 1991 - June 1994
Imperial College London
Field of study
  • Chemistry (Final year concentrating on organic chemistry)

Publications

Publications (154)
Article
Steel swarf is a hazardous waste which is challenging to recycle due to its high content of heavy metals and cutting fluids and is today commonly landfilled. The swarf can contain up to 80% iron and represents a potential secondary raw material for production of reagents like ferric chloride, which can be utilized in wastewater treatment. This work...
Article
Full-text available
The Chalmers Grouped ActiNide EXtraction process is a solvent extraction process for the homogeneous recycling of spent nuclear fuel. The use of TBP for the extraction of tetra- and hexavalent actinides can be problematic for several reasons, including troublesome degradation products causing crud formation, decreased extraction yield and the possi...
Article
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The interactions between tellurium and organic material during a nuclear reactor accident are critical to source term estimations because of the possible formation of volatile species. Reactions taking place in the containment sump are of interest since these can lead to re-volatilization and increase the fission product source term. This paper pre...
Article
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The Chalmers grouped actinide extraction (CHALMEX) process is focused on the co-separation of actinides from all other elements in spent nuclear fuel solution, with the ultimate purpose of transmuting the actinides into shorter-lived and less radiotoxic elements. Based on solvent extraction equilibrium distribution data of actinides and fission pro...
Article
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In the event of a severe nuclear accident, one major concern is the release of radioactive material into the environment causing potential exposure of the general public to radiation. Among the volatile radionuclides are a range of tellurium isotopes. Due to the radioactivity and the volatility of tellurium, it has to be taken into account when ass...
Article
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The solvent extraction of gold, palladium, technetium, indium and rhenium from both mixtures of a deep eutectic solvent with aqueous salt solutions and of two different aqueous salt solutions has been performed. Initially using gold and then the other metals the solvent extraction results were interpreted using an activity coefficient / function eq...
Article
In several industrial Lithium-ion batteries recycling processes, a thermal treatment with oxidative atmosphere is used to separate the battery components and to remove the organic components. This method is often combined with hydrometallurgical processes with the aim to increase the metal recovery rate or to improve the efficiency of the existing...
Article
The reactions of [M(3-C3H5)Br(CO)2(NCMe)2] (M = Mo, W) or [Mo(3-C3H5)(CO)2(PMe2Ph)2] with Na[H2B(mt)2] (mt = methimazolyl) affords the complexes [M(3-C3H5)(CO)2{3-H,S,S’-H2B(mt)2}], the 3-centre, 2-electron B–H–M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with...
Article
The effects of pyrolysis on the composition of the battery cell materials as a function of treatment time and temperature were investigated. A waste of Li-ion batteries was pyrolysed in nitrogen atmosphere at 400˚, 500˚, 600˚, and 700˚C for 30, 60, and 90 minutes. Thermodynamic calculations for the carbothermic reduction of active materials LiCoO2,...
Article
A range of ruthenaboratranes of the form [Ru(CO)L{4-B,S,S’,S”-B(mt)3}] (mt = N-methylmercaptoimidazolyl) have been prepared either by substitution of the PPh3 ligand in [Ru(CO)(PPh3){4-B,S,S’,S”-B(mt)3}] by L (L = PMe2Ph, PMe3, P(OMe)3,...
Article
Distribution ratios of trivalent lanthanide ions in extraction reactions may be affected by the denticity of a solvent extraction ligand for entropic reasons. This hypothesis was tested by studying the reactions of extraction of the lanthanides(III) (La, Nd, Eu, Dy, Er and Yb) from perchlorate media into methyl isobutyl ketone (MIBK) with three str...
Article
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As an emergency action during the Fukushima accident, seawater was used to maintain cooling. To evaluate the effect of the salt on fission-products, sodium chloride, and tellurium were heated together using different ratios in different atmospheres (inert or oxidizing) using thermogravimetric analysis. The experiment under inert conditions showed n...
Article
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A review and discussion of some of the literature on the subject of serious nuclear reactor accidents. This review addresses some biological issues such as the influence of dose rate on the ability of radiation to cause harm, the chemistry of a selection of serious accidents and the behaviour of a series of important fission products and the actini...
Article
During a serious nuclear reactor accident a large fraction of the radioactive iodine in the fuel can escape from the core and subsequently from the plant. While the noble gases in reactor fuel are more mobile than iodine, the iodine is often of greater concern as its chemistry and biology causes it to be more radiotoxic. Iodine has the potential to...
Article
Full-text available
The reaction of Na[H2B(mt)2] (mt = 2-mercapto, 3-methylimidazol-1-yl, methimazolyl)) with [Ru(X)Cl(CO)(PPh3)n] (n = 3 X = H; n = 2 BO2C6H4, SiCl3, SiMe3) affords the complexes [Ru(X)(CO)(PPh3){2-H,S,S’-H2B(mt)2}] and evidence is presented to also support the transient formation of [Ru(X)(CO)(PPh3){2-H,S,S’-H2B(mt)2}] (X = CH=CHPh, Ph) via a simil...
Article
Full-text available
The reaction of diethyl malonate with phthaloyl chloride in acetonitrile in the presence of triethylamine and magnesium chloride results in the formation of the title compound, diethyl 2-(3-oxo-1,3-dihydro-2-benzofuran-1-ylidene)propanedioate, C 15 H 14 O 6 . One of the ester groups of the diethyl malonate fragment is almost coplanar with the isobe...
Article
The complexation of the bismalonamide ligand 2,2'-(1,2-phenylenebis(methylene))bis(N,N,N',N'-tetraethylmalonamide) (L), bearing two C-alkylated N,N,N',N'-tetraethylmalonamide groups onto ortho-xylylene (C6H4(CH2)2) platform, with trivalent lanthanides was investigated both in solid- and solution states. The crystal structures [Nd2(NO3)6L2]·(CH3CN)3...
Article
Progress towards a sustainable industrial process for the recycling of unwanted batteries using a deep eutectic solvent is presented. The effect of lactate anions on the recovery of metals from chloride media by extraction by a lipophilic chloride ionic liquid has been investigated with using solvent extraction experiments with a special emphasis o...
Article
Full-text available
Deep-eutectic solvents (DESs) are used as a promising alternative to aqueous solutions for the recovery of valuable metals from NdFeB magnets. A deep-eutectic solvent based on choline chloride and lactic acid (molar ratio 1:2) was used for the leaching of rare earths and other metals from NdFeB magnets. A process for the separation of Fe, B and Co...
Article
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The rare-earth elements (REEs) are considered as some of the most critical elements in the EU and the USA today. E-scrap, such as end-of-life neodymium magnets, could be a viable secondary source for the recovery of these elements. Neodymium magnets (NdFeB) consist of considerable amounts of Nd, Dy, Pr, and some other REEs, depending on the specifi...
Article
An understanding of the effects of the water content on the solvent extraction of metals from the deep eutetic formed from choline chloride and lactic acid has been obtained. This...
Article
The syntheses and crystal structures of two one-dimensional coordination polymers, [Mn(C5HO2F6)2(C16H20N2)]n (1) and [Mn(C5HO2F6)2(C20H20N2)]n (2), are described, where C5HO2F6⁻ is the hexafluoro acetylacetonate anion, C16H20N2 is 1,6-bis(4-pyridyl)-hexane, and C20H20N2 is 1,4-bis[2-(3-pyridyl)ethyl]-benzene. In both phases, the metal ion lies on a...
Article
Owing to the ever-growing demand and supply problems, rare earth elements (REEs) are now considered to be some of the most critical elements. This has focused attention towards their recovery from end-of-life products and industrial waste streams. A hydrometallurgical approach was carried out to assess the recycling potential of REEs from fluoresce...
Article
Full-text available
Waste electrical and electronic equipment (WEEE) is growing rapidly, and the plastics within WEEE have an important role in fulfilling the recovery and recycling targets defined in the European WEEE Directive. This study considers recycling of WEEE plastics by making a blend of the different plastics instead of separating them. The mechanical and t...
Article
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Solvent extraction experiments relating to the recycling of the transition metals and lanthanides in nickel metal hydride cells are presented. The metal extraction is occurring from a deep eutectic solvent which is formed from chemicals suitable for use in food and related products. While it has been shown that the water content of the DES has a la...
Article
Full-text available
A review of the chemistry occurring inside a nuclear power plant during a serious reactor accident is presented. This includes some aspects of the behavior of nuclear fuel, its cladding, cesium and iodine. This review concentrates on the chemistry of an accident in a water-cooled reactor loaded with uranium dioxide or mixed metal oxide fuel.
Article
Full-text available
Separation of trivalent actinoid (An(III)) and lanthanoid (Ln(III)) ions is extremely challenging due to their similar ionic radii and chemical properties. Poly-aromatic nitrogen compounds acting as tetradentate chelating ligands to the metal ions in the extraction, have the ability to sufficiently separate An(III) from Ln(III). One of these compou...
Article
The crystal structures of three compounds formed from the crystallisation of different copper(II) salts (nitrate, acetate and sulphate) with the new ligand 1,3-bis[2-(4-pyridyl)ethyl]-benzene, C20H20N2 (L) are reported. The anion is incorporated into each structure, but it plays a completely different role in each case: [Cu2L4(NO3)(H2O)2]·3(NO3) (1...
Article
The syntheses and structures of the coordination polymers [Cd(ppeb)2(H2O)2]n·(NO3)2n (1), [Cd(ppeb)2(ClO4)2]n (2), [Cd(opeb)2(NO3)2]n (3) and [Cd(opeb)2(H2O)2]n·(ClO4)2n (4), where ppeb and opeb represent the 1,4- and 1,2-isomers of bis[2-(3-pyridyl)ethyl]-benzene, C20H20N2, respectively, are described. Each structure contains trans-CdO2N4 octahedr...
Article
We explore γ-radiation cross-linking of high vinyl-content low-density polyethylene (LDPE) and its potential use as a high-voltage insulation material. Of the three investigated resins containing 1, 0.5 and 0.17 vinyl groups per 1000 carbons, respectively, only the highest vinyl-content material featured a sufficiently high gel content of more than...
Article
With the rising popularity of fluorescent lighting, simple and efficient methods for the decontamination of discarded lamps are needed. Due to their mercury content end-of-life fluorescent lamps are classified as hazardous waste, requiring special treatment for disposal. A simple wet-based decontamination process is required, especially for streams...
Article
The effect of adding a t-butyl group to the core molecule of CyMe4-BTBP, with the aim of improving solubility in organic diluents, has been studied with regard to the extraction of Am(III) and Eu(III) from HNO3. Synthesis of t-Bu-CyMe4-BTBP is described in detail. Metal nitrates are extracted from nitric acid in the form of 1:2 complexes, M(NO3)3(B...
Article
The thermodynamic parameters (ln KEx, ΔH0 and ΔS0) for the extractions of americium and europium using CyMe4-BTBP in three various diluents (cyclohexanone, hexanol and nitrobenzene) have been studied. The stoichiometry of the complexes was obtained by slope analysis of the distribution ratios of the metals as a function of the ligand concentration....
Article
The rate of americium mass transfer between the aqueous and organic phase in a solvent extraction system has been investigated. The ligand used is CyMe4-BTBP and the diluents are long-chained alcohols. The results are compared with earlier reported data using C5-BTBP as ligand. In the C5-BTBP system the rate of the extraction could be correlated wi...
Article
Full-text available
The title compound, poly[[di­aqua­bis­[1,5-bis­(pyridin-4-yl)pentane-κ2 N:N′]cadmium] bis­(perchlorate) 1,5-bis­(pyridin-4-yl)pentane ethanol mono­solvate], [Cd(C15H18N2)2(H2O)2](ClO4)2·C15H18N2·C2H6O, is a layered coordination polymer built up from highly squashed 44 nets in which the octa­hedral trans-CdO2N4 nodes (Cd site symmetry -1) are linked...
Article
The growing need for materials such as rare earth metals (REMs) has focused attention towards their recovery from various end-of-life products. Fluorescent lamps are considered a viable target, and can be a source of up to six REMs: lanthanum, cerium, europium, gadolinium, terbium, and yttrium. In this study a commercial mix of trialkylphosphine ox...
Article
Full-text available
In this work, stability experiments have been performed on a phenyl trifluoromethyl sulfone based solvent containing 6,6′-bis(5,6-dialkyl-[1,2,4-]triazin-3-yl)-2,2′-bipyridine and tri-butyl phosphate. This solvent is intended to be used in a grouped actinide extraction process for partitioning and transmutation purposes. The distribution ratio for...
Article
Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition to the generally high price of the material, significant amounts of the metals are...
Article
Used nuclear fuel is radiotoxic for mankind and its environment for a long time. However, if it can be transmuted, the radiotoxicity as well as its heat load are reduced. Before a transmutation the actinides within the used fuel need to be separated from the fission, corrosion and activation products. This separation can be achieved by using the li...
Article
A recyclable plastics waste stream of electrical and electronic equipment has previously been found to contain acrylonitrile-butadiene-styrene copolymer (ABS, similar to 40 wt%), high impact polystyrene (HIPS, similar to 40 wt%), polypropylene (PP, similar to 10 wt%) and a rest fraction consisting mainly of other styrene-based thermoplastics. In th...
Article
Methods for the small scale synthesis of I-131 labelled iodine species relevant to severe nuclear accidents in light water reactors have been developed. The introduced methods allow the synthesis of impurity free, volatile, inorganic elemental iodine and volatile, organic iodides such as methyl- and ethyl iodide, as well as butyl iodide, chloroiodo...
Article
Two Group ActiNide EXtraction solvents for the extraction of actinides from used nuclear fuel for transmutation purpose have been compared. The solvent studied more precisely comprises cyclohexanone, tributylphosphate, and a molecule from the bis-triazine bi-pyridine family, while the alternative utilizes di-ethyl-hexyl butyramide instead of tribut...
Article
The formation of volatile alkyl iodides other than methyl iodide during a serious nuclear reactor accident may have radiological significance. The hypothesis that radioactive alkyl iodides, other than methyl iodide, could form from paint solvents under the conditions of a serious nuclear accident in light water reactors (under boiling water reactor...
Article
A Group ActiNide EXtraction (GANEX) separation system for transmutation has been developed, combining CyMe4-BTBP with TBP and cyclohexanone. This new GANEX solvent has proven efficient in actinide extraction but also been found to extract some undesired fission products and corrosion products. Three major fission products were primarily selected fo...
Article
There has been a recent interest in antimony since the availability in readily mined areas is decreasing compared to the amounts used. It is important in many applications such as flame retardants and in the production of polyester, which can trigger an investigation of the leachability of antimony from plastics using different acids. In this paper...
Article
The compositions of three WEEE plastic batches of different origin were investigated using infrared spectroscopy, and the metal content was determined with inductively coupled plasma. The composition analysis of the plastics was based mainly on 14 samples collected from a real waste stream, and showed that the major constituents were high impact po...
Article
Full-text available
In a solvent intended for use within group actinide extraction CyMe4-BTBP and TBP are combined together in cyclohexanone. After irradiating the solvent in acid contact a latency period before extraction reduced the extraction capability of plutonium. This reduction was larger when the solvent was kept in contact with the acid after irradiation. The...
Article
Full-text available
Solvent extraction and the so called BTBP class of ligands can be used for the separation of the actinides from the rest of used nuclear fuel. One troublesome co-extracting element in this separation is silver.Therefore, two different BTBP molecules, having different side groups have been investigated. It was shown that the silver distribution rati...
Article
To enable laboratory work with larger amounts of ²²⁶ Ra and its decay products, e.g. , ²²² Rn and its daughters, these need to be captured in order to avoid unnecessary alpha contamination of the laboratory work space and ventilation systems. In this study, radon gas was pumped through a column filled with the silver exchanged zeolite called “silve...
Article
Research focus within separation for transmutation in Europe today lies in the development of a solvent extraction separation process called GANEX (Group ActiNide EXtraction). In this type of process the actinides should be extracted as a group and separated from the lanthanides and the other fission and corrosion/activation products. One GANEX pro...
Article
The floors, concrete walls and many of the metal surfaces in nuclear power plant containments are coated with zinc primers or paint films to preserve the metal surfaces and simplify decontamination in the containment after the occurrence of a severe nuclear incident or accident. A chemical examination of paint films from different nuclear installat...
Article
It has recently been reported that a cyclohexanone based solvent containing the extractant, CyMe4-BTBP (Bis-Triazine,BiPyridine) together with tri-butyl phosphate intended for use in a GANEX (Group Actinide Extraction) process also extracts the fission product palladium. When cyclohexanone was used as a diluent it was also observed that without any...
Article
The waste from nuclear power plants worldwide has to be isolated from man and his environment for about 100,000 years to equal the levels of natural uranium. If, however, the long-lived actinides could be separated from the spent fuel and transmuted, then the isolation time could be shortened to about 1,000 years. This does, however, require the se...
Chapter
The waste from nuclear power plants has to be isolated from man and his environment for about 100,000 years to be considered safe. It has been suggested that if the long-lived actinides could be separated from the spent fuel and transmuted, the isolation time could be shortened to about 1,000 years. This, however, requires selective separation of p...
Article
Hydrochemical separation processes are one of the methods used for the treatment of spent nuclear fuel. Solvent extraction is also used in many other non-nuclear applications like the mining industry. In the nuclear case, hydrochemical separation processes are already employed in the world today for the recovery of uranium and plutonium. The method...
Article
Full-text available
A GANEX (Group ActiNide EXtraction) separation system for transmutation has been developed. In this separation process the actinides should be extracted as a group from the lanthanides and the fission and corrosion/activation products. This can be achieved by combining BTBP (bis-triazine-bipyridine) with TBP (tri-butyl phosphate) in cyclohexanone....
Article
The complexation of Cm(III) and Eu(III) with 4-t-butyl-6,6'-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine (t-Bu-C2-BTBP) in water/2-propanol solution is studied. With increasing ligand concentration, 1 : 2 complexes [M(t-Bu-C2-BTBP)(2)(H(2)O)](3+) form from the solvated metal ions. The stability constants are log K(Cm(III)) = 11.1 and log K(...
Article
Efficient recovery of minor actinides from a genuine spent fuel solution has been successfully demonstrated by the CyMe4‐BTBP/DMDOHEMA extractant mixture dissolved in octanol. The continuous countercurrent process, in which actinides(III) were separated from lanthanides(III), was carried out in laboratory centrifugal contactors using an optimized f...
Article
The recently developed ligand MF2-BTBP dissolved in cyclohexanone is a promising solvent for the group separation of trivalent actinides(III) from the lanthanides(III). Its high stability against nitric acid has been demonstrated recently. Since the solvent is also exposed to a continuously high radiation level in the counter current process, the r...
Article
The syntheses of a range of poly(methimazolyl)borate -ligated nitrosyl complexes of tungsten and molybdenum are reported, the characterization of which includes the crystal structure determinations of the compounds [W(NO)(CO)2{κ3-S,S′,S′′-HB(mt)3}], [W(NO)(CO)2(PPh3){κ2-S,S′-H2B(mt)2}], and [Mo(NO)(CO)2{κ3-H,S,S′-H2B(mt)2}] (mt = methimazoyl). The...
Article
A synthesis of a safe and effective hydrogenationcatalyst has been developed with used nickel metal hydride electrical cells as the starting material.
Conference Paper
Partitioning and transmutation (P and T) of the long lived nuclides in spent nuclear fuel into short-lived ones is an important step in decreasing the radiotoxicity, volume, and time necessary for storage in a repository. A proper separation of the metals used in the transmutation process is necessary and solvent extraction with different ligands i...
Conference Paper
Different polycyclic molecules containing nitrogen have been developed to be used as extractants in the separation of actinides(III) from lanthanides(III) in the spent nuclear-fuel treatment. During a potential industrial process involving nuclear waste, the extractant will be exposed to high doses of ionizing radiation; hence, the extractant shoul...
Article
The partitioning of minor trivalent actinides (An) from lanthanides (Ln) is one of the challenges in the chemical treatment of nuclear waste. The optimal ligand to carry out the separation of An(III) and Ln(III) using solvent extraction has to meet several important criteria: high selectivity towards the solute, chemical and radiolytic stability, s...
Article
Treatment of [UO2(OTf)(2)] or [UO2I2(thf)(3)] with 1 equiv. of CyMe4BTBP in anhydrous acetonitrile led to the formation of [UO2(CyMe4BTBP)(OTf)(2)] (1) and [UO2(CyMe4BTBP)I-2] (2) which crystallized as the cationic forms [UO2(CyMe4BTBP)(py)][OTf](2) (3) and [UO2I(CyMe4BTBP)][I] (4) in pyridine and acetonitrile, respectively. These compounds are uni...
Article
The reaction of [Ru(CHCH2)Cl(CS)(PPh3)2] with Na[HB(mt)3] (mt = methimazolyl) provides the ruthenaboratrane [Ru(CS)(PPh3){B(mt)3}]. The reaction of [Ru(CO)(PPh3){B(mt)3}] with CO to provide [Ru(CO)2{B(mt)3}] is reversible, while the phosphine-free ruthenaboratranes [Ru(CO)(CNR){B(mt)3}] (R = tBu, C6H3Me2-2,6, C6H2Me3-2,4,6) form irreversibly upon a...
Article
Recently the BTBP‐family of solvating ligands have been studied for their ability to separate trivalent actinides from lanthanides. Five of the BTBPs were evaluated for their ability to extract nickel(II) from aqueous nitrate media into cyclohexanone. It was shown by both solvent extraction and X‐ray diffraction experiments that the BTBPs are capab...
Article
Low doses of gamma radiation were given to four different solvents containing C5-BTBP and CyMe The results were unexpected. The presence of a cyclic molecule as both a side group or diluent seems to keep the extraction of europium almost unaffected by radiolysis, while americium behaves differently from solvent to solvent. The diluent alone does no...
Article
The separation by solvent extraction of 241Am(III) from 152Eu(III), in 1 M NaNO3 weakly acidic (pH 4) aqueous solutions, into dilute (ca. 10−2 M) solutions of triazinylbipyridine derivatives (diethylhemi-BTP or di(benzyloxyphenyl)hemi-BTP) and chlorinated cobalt dicarbollide (COSAN) in 1-octanol or nitrobenzene has been studied. The N-tridentate he...