Extraction-Spectrophotometric Studies on the Ion-Pairing Between Some 2,3,5-Substituted Monotetrazolium Cations and Anions Deriving from 4-(2-Thiazolylazo)resorcinol or 4-(2-Pyridylazo)resorcinol

The ion-pairing between some 2,3,5-substituted monotetrazolium cations (T+) and anions deriving from 4-(2-pyridylazo)resorcinol (PAR) or 4-(2-thiazolylazo)resorcinol (TAR) was studied by water-chloroform extraction and spectrophotometry. The following tetrazolium salts (TS) were used as a source of T+: i) 2,3,5-triphenyl-2H-tetrazolium chloride (TTC); ii) 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT); iii) 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV); and iv) 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT). The spectral characteristics of the extracted species were established at different pH and TS concentration. The composition and stability of the ion-pairs were determined at pH 9, where the extraction of neutral PAR (H2PAR) and TAR (H2TAR) species was negligible. The results showed that the ion-pairs can be expressed with the following formulae (T+)(HTAR–) (where T+ = TT+, MTT+, TV+ or INT+), (T+)(HPAR–) (where T+ = TT+, MTT+ or TV+) and [(INT+)(HPAR–)]2. Relationships involving the molecular masses of the ion-pairs (MIP) or T+ (MT+) and the values of the constants of association (b) or conditional molar absorptivities (e’) were examined, namely Log b = f(Log MIP) and e’ = f(Log MT+). Some practical aspects concerning the investigation of metal complexes with TS-PAR/TS-TAR were discussed

Application of 4-(2-pyridylazo)resorcinol for flotation-spectrophotometric determination of iron

Optimum conditions for flotation-spectrophotometric determination of iron with 4-(2-pyridylazo)resorcinol (PAR) based on a 1:2 FeII-PAR complex were found to be as follows: flotation solvent (chloroform), shaking time (2 min), pH (4.5±0.5), concentration of PAR (2.0×10–4 mol L–1), reducing agent (hydroxylamine hydrochloride), solvent for the floated compound (dimethylsulphoxide, DMSO), wavelength for spectrophotometric measurements (718 nm), and volumes of the organic solvents (5 mL of chloroform and 3 mL of DMSO). Calibration graphs were compared for different volumes of the aqueous phase – 10 mL and 40 mL; the corresponding linear ranges were 0.30–1.3 mg mL–1 and 0.25–1.0 mg mL–1. The iron content was successfully determined in soil samples, reference standard materials (PS-1, COOMET No. 0001-1999 BG, SОD No. 310а-98; PS-2, COOMET No. 0002-1999 BG, SOD No. 311а-98; and PS-3, COOMET No. 0003-1999 BG, SOD No. 312а-98) and zinc sulfide concentrates. KEY WORDS: Iron(II), Fe-PAR complex, Flotation, Spectrophotometry, Soils, Zinc sulfide concentrates Bull. Chem. Soc. Ethiop. 2016, 30(3), 325-332.DOI: http://dx.doi.org/10.4314/bcse.v30i3.

Land use change in Amazonian Dark Earth and Acrisol: responses of organic carbon, organic matter composition and microbial carbon utilisation.

The conversion of tropical forest for cassava cultivation is widely known to decrease the soil organic matter (OM) and nutrient contents of highly weathered soils in the tropics. Amazonian Dark Earth (ADE) might be affected less due to their historical anthropogenic amelioration with e.g. charcoal, ceramics and bones, leading to higher soil OM and nutrient concentrations. In this study, we analysed the effect of land use change on the OM dynamics and its composition under tropical conditions, using ADE and an adjacent Acrisol (ACR) as model systems

Consequences of land use change on soil organic matter composition and C-P relationships in Amazonian Dark Earth and Acrisol.

The conversion of tropical forest for cassava cultivation is widely known to decrease the soil organic matter (OM) and nutrient contents of highly weathered soils in the tropics. Amazonian Dark Earth (ADE) might be more resistant to this process due to their historical anthropogenic amelioration with e.g. charcoal, ceramics and bones, leading to higher soil OM and nutrient concentrations. In this study, we analyzed the effect of land use change on the OM dynamics under tropical conditions and how this is related with P distribution at the microscale, using ADE and an adjacent Acrisol (ACR) as model systems

Isotopic analysis of cyanobacterial nitrogen fixation associated with subarctic lichen and bryophyte species.

Dinitrogen fixation by cyanobacteria is of particular importance for the nutrient economy of cold biomes, constituting the main pathway for new N supplies to tundra ecosystems. It is prevalent in cyanobacterial colonies on bryophytes and in obligate associations within cyanolichens. Recent studies, applying interspecific variation in plant functional traits to upscale species effects on ecosystems, have all but neglected cryptogams and their association with cyanobacteria. Here we looked for species-specific patterns that determine cryptogam-mediated rates of N-2 fixation in the Subarctic. We hypothesised a contrast in N-2 fixation rates (1) between the structurally and physiologically different lichens and bryophytes, and (2) within bryophytes based on their respective plant functional types. Throughout the survey we supplied N-15-labelled N-2 gas to quantify fixation rates for monospecific moss, liverwort and lichen turfs. We sampled fifteen species in a design that captures spatial and temporal variations during the growing season in Abisko region, Sweden. We measured N-2 fixation potential of each turf in a common environment and in its field sampling site, in order to embrace both comparativeness and realism. Cyanolichens and bryophytes differed significantly in their cyanobacterial N-2 fixation capacity, which was not driven by microhabitat characteristics, but rather by morphology and physiology. Cyanolichens were much more prominent fixers than bryophytes per unit dry weight, but not per unit area due to their low specific thallus weight. Mosses did not exhibit consistent differences in N-2 fixation rates across species and functional types. Liverworts did not fix detectable amounts of N-2. Despite the very high rates of N-2 fixation associated with cyanolichens, large cover of mosses per unit area at the landscape scale compensates for their lower fixation rates, thereby probably making them the primary regional atmospheric nitrogen sink

An extraction-chromogenic system for vanadium(IV,V) based on 2,3-dihydroxynaphtahlene

A liquid-liquid extraction-chromogenic system for vanadium(IV, V) containing 2,3-dihydroxynaphtahlene (DN), 2,3,5-triphenyl-2H-tetrazolium chloride (TTC), water and chloroform was studied in detail. When the vanadium is in the oxidation state of IV, the extracted species are aggregates containing three 1:2:1 (V:DN:TTC) ion-pair units composed of triphenyltetrazolium cations (TT+) and chelate anions {[VIVO(DN)(DNH)]− (I) and/or [VIV(OH)(DN)2]− (II)}. When the initial oxidation state of vanadium is V and the DN concentration is high, vanadium(V) is reduced by DN to a lower oxidation state, V(IV). However, at low DN concentration, vanadium(V) can enter the organic phase as a part of an ion-pair consisting of TT+ and [VVO2(DN)]− (III). The ground-state equilibrium geometries of the anions I, II, and III were optimized by quantum chemical calculations using BLYP/6-31++G⋆. The following characteristics were determined under the optimum conditions for VIV extraction: absorption maximum λmax = 333 nm, molar absorptivity ε333= 2.1x104 dm3 mol−1 cm−1, Sandell’s sensitivity SS = 2.4 ng cm−2, and fraction extracted E = 98%. The conditional extraction constant was calculated by two independent methods. The calibration graph was linear in the range 0.1-3.1 μg cm−3 (R2=0.9994) and the limit of detection was 0.03 μg cm−3

Environmental drivers of carbon and nitrogen isotopic signatures in peatland vascular plants along an altitude gradient

Peatlands are important sinks of atmospheric carbon (C) that, in response to climate warming, are undergoing dynamic vegetation succession. Here we examined the hypothesis that the uptake of nutrients by different plant growth forms (PGFs) is one key mechanism driving changes in species abundance in peatlands. Along an altitude gradient representing a natural climate experiment, we compared the variability of the stable C isotope composition (δ13C) and stable nitrogen (N) isotope composition (δ15N) in current-year leaves of two major PGFs, i.e. ericoids and graminoids. The climate gradient was associated with a gradient of vascular plant cover, which was parallelled by different concentrations of organic and inorganic N as well as the fungal/bacterial ratio in peat. In both PGFs the 13C natural abundance showed a marginal spatial decrease with altitude and a temporal decrease with progression of the growing season. Our data highlight a primary physical control of foliar δ13C signature, which is independent from the PGFs. Natural abundance of foliar 15N did not show any seasonal pattern and only in the ericoids showed depletion at lower elevation. This decreasing δ15N pattern was primarily controlled by the higher relative availability of organic versus inorganic N and, only for the ericoids, by an increased proportion of fungi to bacteria in soil. Our space-for-time approach demonstrates that a change in abundance of PGFs is associated with a different strategy of nutrient acquisition (i.e. transfer via mycorrhizal symbiosis versus direct fine-root uptake), which could likely promote observed and predicted dwarf shrub expansion under climate change