Behaviour of complexes of f–elements in the environment – An experimental and theoretical analysis

• Theoretical quantum chemical treatment of lanthanide and actinide complexes.
• Environmental analysis.
• Biogeochemical reactions in solution and onto inorganic surfaces.
• Experimental mass spectrometric correlation analysis.
• Molecular structure – thermodynamics relationship.

The paper provides a comprehensive study of lanthanide and actinide complexes to a matter of key area in the field of the chemistry, i.e. environmental analytical chemistry. The content has involved: (i) solution and sorption behaviour of lanthanides (Lnn+, Ln = Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Py, Ho, Er, Tm, Yb and Lu) onto Y(O)O(H) minerals (Y = Fe, Mn or Si); (ii) ligand exchange processes with participation of inorganic OH−, F−, Cl−, Br−, SO42−, SO32−, IO3−, NO32−, CO32− and/or HCO3− ligands as well as mixed ligand complexes, including solvent molecules such as {[LnOR]2+}, {[Ln(OR)2]+} (R = CH3OH, CH3CH2CH2OH) and {[Ln(CH3CN)x(H2O)z]3+} (x = 6–8, z = 0–4); (iii) the actinide speciation has involved different oxidation states (+4)–(+6) and ions {[UOH]3+}, {[UX]3+} (X = F or Cl), {[UFx]y+/-} (x = 2–6, y = 0–2), {[U(CO3)x]y-} (x = 4 or 5, y = 4 or 6), {[U(SO4)]2+], {[U(NO3)]3+}, {[U(NO3)2]2+}, [[UO2(CO3)3]5-}, {[(UO2)x(OH)z]y+/-} (x = 1–4, y = 1 or 2, z = 1–7), {[UO2Fx]y+/-} (x = 1–4, y = 1 or 2), {[UO2(CO3)x]y-} (x = 2, or 3, y = 2, or 4), {[(UO2)2(CO3)(OH)3]-}, {[(UO2)3O(OH)2(HCO3)]+}, {[(UO2)11(CO3)6(OH)12]2-}, {[UO2(SO4)x]y-}, (x = 2 or 3, y = 2 or 4), {[UO2SiO(OH)3]+}, {[AnCx]y+/-} (x,y = 1 and 2), {[CAnH]+/−}, {[CxAny]0} (x,y = 2 and 3), {[AnHx]y+} (x = 1–3, y = 0–5), {[AnXn]m+/-} (n = 1–6, m = 1–4, X = F−, Br−, I−), {[AnOxFz]y+/-} (x, z = 1 or 2, y = 0, 1 and 2), {[AnNx]y+} (x = 1 and 2), {[AnxOz(OH)n]y+/-} (x = 1–3, z = 1–4, y = 0, 1 or 2, n = 0 or 1) and Ann+ (n = 0–6) at An = Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No and Lr, respectively. Correlation analysis between thermodynamic parameters, accounting for different surface interactions of adsorbed species and experimental mass spectrometric data, including liquid, semi–liquid and solid–state measurements in a large set of experimental conditions such as pH = 2–13, low and intermediate ionic strength, solvent type, ε = 0–78.0, variety of solvent proton accepting and donating numbers and T = 25–400 °C has carried out.

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