Temporal variation of iodine in Danish groundwater

Iodine is an essential element for human health, and both high and low iodine intake could have negative health outcomes. The spatial variation of iodine in Danish groundwater has been studied before, but to the author’s knowledge, this is the first time that the temporal variation is characterised. Nationwide data from the Danish groundwater monitoring programme (GRUMO) were analysed between 2011 and 2021, including 2924 samples from 1242 well screens at 893 wells. The sampling frequency varied and so the robust coefficient of variation (rCV) was calculated for 930 (75%) of well screens, and time-series analysis was performed for 23 (2%). Key findings are (1) iodine in Danish groundwater varies over time (0–124%, median = 10%), (2) in one quarter of the well screens rCV exceeds 20% and (3) this variation cannot be attributed solely to analytical uncertainty at 14% of the well screens. The impact of temporal variation of iodine in Danish drinking water of groundwater origin should be evaluated in future exposure or epidemiological studies with respect to the study goal, location and time period. Since the temporal variation could not be quantified over the entire concentration range, monitoring of iodine in Danish groundwater should continue

Continuous synthesis of doped layered double hydroxides in a meso-scale flow reactor

Layered double hydroxides are a class of low-cost structured nanomaterials with many potential applica-tions in environmental catalysis and sustainable technologies. Their large-scale use is hindered by the chal-lenge of reproducible synthesis at scale. Here we report a general, readily scalable process for the repro-ducible synthesis of transition metal doped hydrotalcites using a two-step process: co-precipitation in a mm-scale (meso-scale) continuous flow reactor, followed by aging. We have shown that co-precipitation in flow at a residence time close to the micromixing time affords good control of particle formation. Re-producible synthesis allowed us, for the first time, to investigate the formation of the pore morphology of hydrotalcites and their thermal stability as a function of metal doping. The obtained samples exhibited sur-face areas (80-150 m2 g-1) higher than those typically attained in batch syntheses, with very low standard deviation between the samples, a high degree of crystallinity and small crystallite sizes, in the range of 9.5-11.9 nm, depending on composition. A systematic characterization allowed us to elucidate the mechanism of the pore morphology formation: the crystallites were found to agglomerate into disk-like platelets, whereas the pore structure of the hydrotalcites is formed by agglomeration of the platelets.National Research Foundation, Singapor

Acceptorless Amine Dehydrogenation and Transamination Using Pd-Doped Hydrotalcites

The acceptorless dehydrogenation of acyclic secondary amines is a highly desirable but still elusive catalytic process. Here we report the synthesis, characterization, and activity of Pd-doped hydrotalcites (Pd-HTs) for acceptorless dehydrogenation of both primary and secondary amines (cyclic and acyclic). These multifunctional catalysts comprise Brønsted basic and Lewis acidic surface sites that stabilize Pd in 0, 2 + , and 4 + oxidation states. Pd speciation and corresponding catalytic performance is a strong function of metal loading. High activity is observed for the dehydrogenation of secondary aliphatic amines to imines, and N-heterocycles, such as indoline, 1,2,3,4-tetrahydroquinoline, and piperidine, to aromatic compounds. Oxidative transamination of primary amines is achieved using low Pd loading (0.5 mol %), without the need for oxidants. The relative yields of secondary imines afforded are consistent with trends for calculated free energy of reaction, while yields for transamination products correspond to the electrophilicity of primary imine intermediates. Reversible amine dehydrogenation and imine hydrogenation determine the relative selectivity for secondary imine/amine products. Poisoning tests evidence that Pd-HTs operate heterogeneously, with negligible metal leaching. Catalysts retain over 90% of activity over six reuse cycles, but do suffer some selectivity loss, attributed to changes of Pd phases

[(1,2,5,6-η)-Cyclo­octa-1,5-diene]bis­(1-isopropyl-3-methyl­imidazolin-2-yl­idene)rhodium(I) tetra­fluorido­borate

In the title compound, [Rh(C8H12)(C7H12N2)2]BF4, the square-planar Rh complex cation and the BF4 − anion are both bis­ected by a crystallographic twofold rotation axis. The Rh and B atoms lie on this axis and all others are in general positions. In the crystal, two unique C—H⋯F hydrogen-bonding inter­actions are present, which involve both imidazolin-2-yl­idene H atoms. They form two separate C(5) motifs, the combination of which is a rippled hydrogen-bonded sheet structure in the ab plane

Electronic Effects of Support Doping on Hydrotalcite-Supported Iridium N-Heterocyclic Carbene Complexes

The electronic effects of supports on immobilized organometallic complexes impact their activity and lifetime, yet remain poorly understood. Here we describe a systematic study of the support effects experienced by an organometallic complex immobilized on doped hydrotalcite-like materials. To that end, we describe the synthesis and characterization of the first organometallic species immobilized on a palette of doped hydrotalcites via sulfonate linkers. The organometallic species consists of iridium N-heterocyclic carbene (NHC) carbonyl complex ([Na][Ir-(NHC-Ph-SO3)2(CO)2]), a highly active molecular catalyst for transfer hydrogenation of glycerol. The hydrotalcite supports are composed of Al, Mg, and a compatible transition-metal dopant (Fe, Cu, Ni, Zn). The materials were characterized extensively by STEM, XPS, TGA, PXRD, FT-IR, N2 desorption, ICP-AES, TPD, and microcalorimetry to probe the morphology and electronic properties of the support and elucidate structure–property relationships

Lithium in drinking water and incidence of suicide:A nationwide individual-level cohort study with 22 years of follow-up

Suicide is a major public health concern. High-dose lithium is used to stabilize mood and prevent suicide in patients with affective disorders. Lithium occurs naturally in drinking water worldwide in much lower doses, but with large geographical variation. Several studies conducted at an aggregate level have suggested an association between lithium in drinking water and a reduced risk of suicide; however, a causal relation is uncertain. Individual-level register-based data on the entire Danish adult population (3.7 million individuals) from 1991 to 2012 were linked with a moving five-year time-weighted average (TWA) lithium exposure level from drinking water hypothesizing an inverse relationship. The mean lithium level was 11.6 μg/L ranging from 0.6 to 30.7 μg/L. The suicide rate decreased from 29.7 per 100,000 person-years at risk in 1991 to 18.4 per 100,000 person-years in 2012. We found no significant indication of an association between increasing five-year TWA lithium exposure level and decreasing suicide rate. The comprehensiveness of using individual-level data and spatial analyses with 22 years of follow-up makes a pronounced contribution to previous findings. Our findings demonstrate that there does not seem to be a protective effect of exposure to lithium on the incidence of suicide with levels below 31 μg/L in drinking water

Analysis of the geological control on the spatial distribution of potentially toxic concentrations of As and F- in groundwater on a Pan-European scale

The distribution of the high concentrations of arsenic (As) and fluoride (F-) in groundwater on a Pan-European scale could be explained by the geological European context (lithology and structural faults). To test this hypothesis, seventeen countries and eighteen geological survey organizations (GSOs) have participated in the dataset. The methodology has used the HydroGeoToxicity (HGT) and the Baseline Concentration (BLC) index. The results prove that most of the waters considered in this study are in good conditions for drinking water consumption, in terms of As and/or F- content. A low proportion of the analysed samples present HGT≥ 1 levels (4% and 7% for As and F-, respectively). The spatial distribution of the highest As and/or F- concentrations (via BLC values) has been analysed using GIS tools. The highest values are identified associated with fissured hard rock outcrops (crystalline rocks) or Cenozoic sedimentary zones, where basement fractures seems to have an obvious control on the distribution of maximum concentrations of these elements in groundwaters.This research was co-funded by the European Union’s Horizon 2020 research and innovation program (GeoERA HOVER project) under grant agreement number 731166. D. Voutchkova, B. Hansen, and J. Schullehner were also supported by Innovation Fund Denmark (funding agreement number 8055- 00073B). N. Rman participation was supported by the Slovenian Research Agency, research program P1-0020 Groundwaters and Geochemistry. A. Felter, J. Cabalska and A. Mikołajczyk participation was supported by the Polish Ministry of Education and Science. E. Giménez-Forcada is grateful for the support received from the CIPROM/2021/032 Project. Valencian Government. University of Valencia (Spain)

Dietary mineral supplies in Malawi: spatial and socioeconomic assessment

Background Dietary mineral deficiencies are widespread globally causing a large disease burden. However, estimates of deficiency prevalence are often only available at national scales or for small population sub-groups with limited relevance for policy makers. Methods This study combines food supply data from the Third Integrated Household Survey of Malawi with locally-generated food crop composition data to derive estimates of dietary mineral supplies and prevalence of inadequate intakes in Malawi. Results We estimate that >50 % of households in Malawi are at risk of energy, calcium (Ca), selenium (Se) and/or zinc (Zn) deficiencies due to inadequate dietary supplies, but supplies of iron (Fe), copper (Cu) and magnesium (Mg) are adequate for >80 % of households. Adequacy of iodine (I) is contingent on the use of iodised salt with 80 % of rural households living on low-pH soils had inadequate dietary Se supplies compared to 55 % on calcareous soils; concurrent inadequate supplies of Ca, Se and Zn were observed in >80 % of the poorest rural households living in areas with non-calcareous soils. Prevalence of inadequate dietary supplies was greater in rural than urban households for all nutrients except Fe. Interventions to address dietary mineral deficiencies were assessed. For example, an agronomic biofortification strategy could reduce the prevalence of inadequate dietary Se supplies from 82 to 14 % of households living in areas with low-pH soils, including from 95 to 21 % for the poorest subset of those households. If currently-used fertiliser alone were enriched with Se then the prevalence of inadequate supplies would fall from 82 to 57 % with a cost per alleviated case of dietary Se deficiency of ~ US$ 0.36 year−1. Conclusions Household surveys can provide useful insights into the prevalence and underlying causes of dietary mineral deficiencies, allowing disaggregation by spatial and socioeconomic criteria. Furthermore, impacts of potential interventions can be modelled