Jason K. Reynolds

Self-assembly of an imidazolate-bridged FeIII/CuII heterometallic cage

A rare, discrete, mixed-valent, heterometallic Fe(III)/Cu(II) cage, [Cu6Fe8L8](ClO4)12·χsolvent (H3L = tris{[2-{(imidazole-4-yl)methylidene}amino]ethyl}amine), was designed and synthesized via metal-ion-directed self-assembly with neutral tripodal metalloligands. The formation of this coordination cage was demonstrated by X-ray crystallography, ESI mass spectrometry, FT-IR, and UV-vis-NIR spectroscopy.

Tripuhyite and schafarzikite: two of the ultimate sinks for antimony in the natural environment

Abstract Studies of the stability of the oxides schafarzikite, FeSb2O4, and tripuhyite, FeSbO4, have been undertaken to clarify the roles these secondary minerals may have in determining the dispersion of antimony in oxidizing environments. Solubilities were determined at 298.15 K in aqueous HNO3, and these data were used to calculate values of ∆Gf⊖ at the same temperature. The derived ∆Gf⊖(s, 298.15 K) values for FeSb2O4 and FeSbO4 are −959.4±4.3 and −836.8±2.2 kJ mol−1, respectively. These results have been compared with electrochemically derived data, extrapolated from 771−981 K. The present study shows conclusively that although the mobility of Sb above the water table is limited by simple Sb(III) and Sb(V) oxides and stibiconite-group minerals, depending upon the prevailing redox potential and pH, tripuhyite is an important ultimate sink for Sb in the supergene environment. It is highly insoluble even in strongly acidic conditions and its anomalous stability at ambient temperatures causes the common mineral goethite, FeOOH, to react to form tripuhyite at activities of Sb(OH)5(aq) as low as 10−11. The comparatively limited numbers of reported occurrences of tripuhyite in the supergene zone are almost certainly due to the fact that its physical properties, especially colour and habit, are remarkably similar to those of goethite. In contrast, the small number of reported occurrences of schafarzikite can be related to its decomposition to tripuhyite as redox potentials rise at the top of the supergene zone and the fact that it decomposes to sénarmontite, Sb2O3, in acidic conditions, releasing Fe2+ ions into solution. In general, the findings confirm the immobility of Sb in near-surface conditions. Geochemical settings favouring the formation of the above minerals have been assessed using the results of the present study and data from the literature.

A large spin-crossover [Fe 4 L 4 ] 8+ tetrahedral cage

A large discrete face-capped tetranuclear iron(II) cage, [Fe4L4](BF4)8·n(solvent), was synthesised via metal-ion directed self-assembly. The cage is formed from a rigid tritopic ligand that incorporates chelating imidazole-imine functional groups. The cage displays temperature induced spin-crossover and LIESST effects and is amongst the largest iron(II) tetrahedral cages with such properties reported. The synthesis, structure and magnetic properties of this new metallo-cage are presented.

Agricultural acid sulfate soils: a potential source of volatile sulfur compounds?

Environmental context. Acid sulfate soils are important contributors to global environmental problems. Agricultural acid sulfate soils have recently been shown to emit sulfur dioxide, an important gas in global issues of acid rain, cloud formation and climate change. This emission is surprising because these soils tend to be wet and the gas is extremely water-soluble. The potential origins of this gas are not yet understood within the context of acid sulfate soils. Our new study reports the measurement of two potential precursors of sulfur dioxide, dimethylsulfide and ethanethiol, from both a natural and an agricultural acid sulfate soil in eastern Australia. Abstract. Most agricultural soils are generally considered to be a sink for sulfur gases rather than a source; however, recent studies have shown significant emissions of sulfur dioxide and hydrogen sulfide from acid sulfate soils. In the current study, acid sulfate soil samples were taken in northern New South Wales from under sugarcane cropping, as well as from an undisturbed nature reserve. Using gas chromatography/flame photometric detection in conjunction with headspace solid-phase microextraction, we have now determined that these soils are a potential source of the low molecular weight volatile sulfur compounds, dimethylsulfide and ethanethiol. Although the mechanism for their production remains unclear, both compounds are important in the transfer and interconversions of atmospheric and terrestrial sulfur. Therefore, these novel findings have important implications for refining local and regional atmospheric sulfur budgets, as well as for expanding our understanding of sulfur cycling within acid sulfate soils and other sediments.

3d transition metal complexes with a julolidine–quinoline based ligand: structures, spectroscopy and optical properties

A Schiff base type ligand with the combination of the julolidine and the quinoline groups has been reported as a potential chemosensor in detecting the cobalt(II) ion among other heavy and transition metal ions in solution. However, no crystal structure of such a ligand with any metal ions has been reported. In this work, its complexation with 3d transition metal ions (Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)) has been investigated with five new complexes being synthesised, and spectroscopically and structurally characterised. [Mn2L2(CH3OH)2(CH3COO)2]·CH3OH (1) {HL (C22H21N3O) = ((E)-9-((quinolin-8-ylimino)methyl)-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-8-ol)} shows a dinuclear structure with two Mn : L : acetate (1 : 1 : 1) units bridged by two methanol molecules. [CoL2(NO3)]·CH3OH·H2O (2) and [NiL2]·H2O (3) exhibit mononuclear structures with a Co : L or Ni : L ratio of 1 : 2. [CuL(CH3COO)]·1/3CH3OH (4) demonstrates a mononuclear structure and the Cu ion has a square planar coordination polyhedron with a L ligand and a highly non-symmetrical acetate anion. [Zn2L2(CH3COO)2]·CH3OH (5) has two types of dinuclear units, both with two ZnL units bridged by two acetate anions but in three different bridging coordination modes. Their vibrational modes, absorption and photoluminescence properties have also been investigated.

Field-based measurements of sulfur gas emissions from an agricultural coastal acid sulfate soil, eastern Australia

The emissions of biogenic hydrogen sulfide (H2S) and sulfur dioxide (SO2) play important roles in the global atmospheric sulfur (S) cycle. Field-based investigations using ultraviolet fluorescence spectroscopy show that drained acid sulfate soils (ASS) are a potentially unaccounted source of biogenic H2S and SO2. Significant diurnal variations were evident in SO2 fluxes, with average daytime measurements 9.3–16.5-fold greater than night-time emissions. Similar diurnal patterns in H2S fluxes were observed but proved statistically insignificant. The results from simultaneously collected micrometeorological measurements suggest that emissions of SO2 and H2S are most likely occurring via different processes. The SO2 fluxes are closely linked to surface soil temperature and moisture content, whereas H2S is constantly emitted from the land surface at the two study sites. Drained ASS are most likely mapped as agricultural lands rather than drained backswamps. Therefore, these areas are likely to be assigned H2S and SO2 flux values of zero in greenhouse gas species inventories. These findings suggest a need to expand these measurements to other drained ASS areas to refine regional (and possibly global) atmospheric S budgets. Further research is necessary to elucidate the sources of measured S compounds, and specifically whether they are limited to individual agricultural drainage patterns in ASS.

Treatment of drainage from acidic canelands using a constructed wetland

This paper describes trials of a constructed freshwater wetland to treat highly acidic drainage from acid Sulfate soil in a sugarcane farm. A constructed freshwater wetland was used to treat acidic discharge from drained acid sulfate soils on a sugar cane farm in the Tweed River flood plain, northern New South Wales (NSW). The bunded 1.44 ha wetland was laser levelled into 6 segmented bays with an overall hydraulic gradient of 0.13%. Water retention time varies between 19 and 82 days dependent on the prevailing evapotranspiration rate. The wetland, which receives about 12% of runoff from a hydraulically isolated 100 ha sugarcane area by pumping, is designed to treat the highly acidic groundwater-dominated recession phase of drainage with large concentrations of dissolved aluminium, iron and manganese. Common couch grass (Cynodon dactylon) and Eleocharis reeds were established in the wetland by natural recruitment. Transects of water quality wetland during filling and while in operation revealed that pH increased while electrical conductivity (EC), dissolved oxygen (DO), redox potential (RP), dissolved sulfate, total potential and total actual acidity (TPA and TAA) decreased dramatically through the wetland. Iron oxyhydroxide flocks are deposited in the inlet bay of the wetland and the redox-pH relation is consistent with ferrolysis. As water moves further into the wetland it is titrated by the organic matter present, resulting in the reduction of protonic acidity, sulfate, dissolved metal concentrations and EC. The advantages and disadvantages of using the wetland as a practical method to treat drainage within a farming system are discussed. The wetland successfully treated acid drainage.

Dinuclear complexes of europium(III) and gadolinium(III) ions with a julolidine–quinoline-based tridentate ligand

Abstract The reaction of europium(III) or gadolinium(III) acetates with a Schiff base ligand {HL (C22H21N3O) = ((E)-9-((quinolin-8-ylimino)methyl)-1,2,3,5,6,7-hexahydropyrido[3,2,1-ij]quinolin-8-ol)} in methanol affords two dinuclear complexes which have been characterized by powder X-ray diffraction, Raman spectroscopy, scanning electron microscope–electron dispersive spectroscopy, absorption and emission spectroscopies as well as single-crystal X-ray diffraction. [Eu2L2(CH3COO)4(CH3OH)2] (1) and [Gd2L2(CH3COO)4(CH3OH)2] (2) are iso-structures, each consisting of two M : L : CH3COO : CH3OH (1 : 1 : 1 : 1) units bridged by two acetate anions with the metal center in a distorted capped square antiprismatic coordination geometry. Their vibration modes, electronic structures, and photoluminescent properties are reported.

Laboratory study of impacts of concrete fragment sizes on wetland water chemistry

Abstract This study investigated the effects of urban concrete materials, of different particle sizes, immersed in water through a laboratory-based experiment. Water was sourced from a high conservation-value wetland (Blue Mountains upland swamp). Prior to the experiment, wetland water was dilute (32.5 μS/cm), acidic (pH 5.3) and had detectable major ion concentrations of only sodium and chloride. Water was exposed to three treatments of different concrete fragment sizes (whole, crushed and fine). All treatments increased conductivity and pH and also resulted in modified ionic composition where calcium, potassium, hydroxide, carbonate and sulphate were recorded at much high levels. The extent and speed of water chemistry changes was linked to the particle size of the concrete. The results of this study support the hypothesis that concrete can be an environmentally hazardous material influencing water quality in urban catchments.

CCDC 1489722: Experimental Crystal Structure Determination

Related Article: Li Li, Alexander R. Craze, Daniel J. Fanna, Aidan J. Brock, Jack K. Clegg, Leonard F. Lindoy, Janice R. Aldrich-Wright, Jason K. Reynolds, Feng Li|2017|Polyhedron|125|44|doi:10.1016/j.poly.2016.08.049