Phase transition in K2Cd2(SO4)3: Order parameter and microscopic distortions

The transition from P2₁3(T ⁴) to P2₁2₁2₁(D ₂ ⁴ ) in the langbeinite K₂Cd₂(SO₄)₃ has been analyzed using group theoretical methods and previously published structural data above and below the transition. We find that because the transition is strongly first-order, the primary-order parameter has relatively large values at the transition temperature, and higher order terms which involve the order parameter, the strain, and the coupling of the two must be included in the Landau expansion for the free energy. Complex displacements occur at the transition for all atoms of the unit cell, but these displacements can be resolved into contributions which can be shown from symmetry considerations to transform as the _{2 3} irrep of P2 ₁ 3(T ⁴) as well as contributions from symmetry-preserving displacements which transform under the irrep ₁. Therefore, the transition is not a simple one and involves sulfate rotations and cadmium and potassium ion displacements.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Marine debris review for Latin America and the wider Caribbean region: from the 1970s until now, and where do we go from here?

The available literature on marine debris from Latin America and the Wider Caribbean Region was collected and linked, reviewing their methodologies and principal results (quantities, composition and spatial-temporal patterns). The study region comprises 52 coastal countries of which only 14 had registers of works on marine debris. A total of 70 works were available and 69 had their full contents accessed. Brazil dominated the available literature with 70% of the documents. Beaches were the most studied environment, and plastics the prevalent form of contamination in the whole region. The exposure of marine biota (species, type of contact, consequences) was highlighted. The studied region, although still little exploited by this sort of research, shows the same contamination patterns observed world-wide. We also contacted 40 researchers in the area, collecting scientific contributions, opinions and suggestions for improvement of this research field. Further advances and new (urgently needed) lines of research are also discussed.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are: