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We present the effect of sodium ions (Na+) on the nucleation process and phase selectivity for the formation of hexagonal molybdenum trioxide crystals (h-MoO3). The phase selectivity during the reaction is attributed to the interaction of Na+ with the molecules in our precursor solution formed by metallic molybdenum dissolved in a mix of hydrochloric and nitric acids. The vibrational characteristics of the precursor solutions were studied by Raman spectroscopy in combination with density functional theory modeling, showing the presence of [MoO2Cl3(H2O)] ions within the solutions. The symmetric stretching vibration of the Mo-O bonds found at 962 cm-1 in [MoO2Cl3(H2O)]- proved that the addition of Na+ (in the form of dissolved NaCl) to the precursor solutions resulted only in an electrostatic interaction with the aquo (H2O) and chloro (Cl-) ligands in the complex. After heating the precursor solutions, X-ray diffraction, Raman spectroscopy, and scanning electron microscopy of the obtained powders showed that adding NaCl contributed to the phase selectivity of the reaction, with the Na+ ions playing a vital role in the formation of h-MoO3 over other crystalline phases. Based on the nature of the molybdenum complexes found in the precursor solutions and the structural characteristics of the powders, a formation mechanism to obtain h-MoO3 is proposed. Additionally, the phase stability of the h-MoO3 crystals was studied by calorimetry techniques showing that h-MoO3 transforms to a-MoO3 at ~649 K. These results provide important insights into phase control to selectively form hexagonal MoO3. 

Abstract. Annually laminated lake sediment can track paleoenvironmental change at high resolution where alternative archives are often not available. However,information about the chronology is often affected by indistinct and intermittent laminations. Traditional chronology building struggles with thesekinds of laminations, typically failing to adequately estimate uncertainty or discarding the information recorded in the laminations entirely,despite their potential to improve chronologies. We present an approach that overcomes the challenge of indistinct or intermediate laminations andother obstacles by using a quantitative lamination quality index combined with a multi-core, multi-observer Bayesian lamination sedimentation modelthat quantifies realistic under- and over-counting uncertainties while integrating information from radiometric measurements (210Pb,137Cs, and 14C) into the chronology. We demonstrate this approach on sediment of indistinct and intermittently laminatedsequences from alpine Columbine Lake, Colorado. The integrated model indicates 3137 (95 % highest probability density range: 2753–3375) varveyears with a cumulative posterior distribution of counting uncertainties of −13 % to +7 %, indicative of systematic observerunder-counting. Our novel approach provides a realistic constraint on sedimentation rates and quantifies uncertainty in the varve chronology byquantifying over- and under-counting uncertainties related to observer bias as well as the quality and variability of the sediment appearance. The approachpermits the construction of a chronology and sedimentation rates for sites with intermittent or indistinct laminations, which are likely moreprevalent than sequences with distinct laminations, especially when considering non-lacustrine sequences, and thus expands the possibilities ofreconstructing past environmental change with high resolution.