Dissolution rates of earthworm-secreted calcium carbonate

The dissolution of CaCO3 granules secreted by earthworms in soil leaching columns was governed by soil pH and exchange sites available for Ca. Results indicate that granules could last for significant periods of time in soils and that, therefore, granules could be an important source of soil calcite.

Soil pH governs production rate of calcium carbonate secreted by the earthworm Lumbricus terrestris

Lumbricus terrestris earthworms exposed to 11 soils of contrasting properties produced, on average, 0.8 ± 0.1 mgCaCO3 earthworm−1 day−1 in the form of granules up to 2 mm in diameter. Production rate increased with soil pH (r2 = 0.68, p < 0.01). Earthworms could be a significant source of calcite in soils.

Electron spin resonance study of puff-resolved free radical formation in mainstream cigarette smoke

Puff-by-puff resolved gas phase free radicals were measured in mainstream smoke from Kentucky 2R4F reference cigarettes using ESR spectroscopy. Three spin-trapping reagents were evaluated: PBN, DMPO and DEPMPO. Two procedures were used to collect gas phase smoke on a puff-resolved basis: i) the accumulative mode, in which all the gas phase smoke up to a particular puff was bubbled into the trap (i.e., the 5th puff corresponded to the total smoke from the 1st to 5th puffs). In this case, after a specified puff, an aliquot of the spin trap was taken and analysed; or, ii) the individual mode, in which the spin trap was analysed and then replaced after each puff. Spin concentrations were determined by double-integration of the first derivative of the ESR signal. This was compared with the integrals of known standards using the TEMPO free radical. The radicals trapped with PBN were mainly carbon-centred, whilst the oxygen-centred radicals were identified with DMPO and DEPMPO. With each spin trap, the puff-resolved radical concentrations showed a characteristic pattern as a function of the puff number. Based on the spin concentrations, the DMPO and DEPMPO spin traps showed better trapping efficiencies than PBN. The implication for gas phase free radical analysis is that a range of different spin traps should be used to probe complex free radical reactions in cigarette smoke.

Production and dissolution rates of earthworm-secreted calcium carbonate

Earthworms secrete granules of calcium carbonate. These are potentially important in soil biogeochemical cycles and are routinely recorded in archaeological studies of Quaternary soils. Production rates of calcium carbonate granules by the earthworm Lumbricus terrestris L. were determined over 27 days in a range of soils with differing chemical properties (pH, organic matter content, water holding capacity, bulk composition, cation exchange capacity and exchangeable cations). Production rate varied between soils, lay in the range 0–0.043 mmolCaCO3 (0–4.3 mg) earthworm−1 d−1 with an average rate of 8 × 10−3 mmolCaCO3 (0.8 mg) earthworm−1 d−1 and was significantly correlated (r = 0.68, P ≤ 0.01) with soil pH. In a second experiment lasting 315 days earthworms repeatedly (over periods of 39–57 days) produced comparable masses of granules. Converting individual earthworm granule production rates into fluxes expressed on per hectare of land per year basis depends heavily on estimates of earthworm numbers. Using values of 10–20 L. terrestris m−2 suggests a rate of 18– 3139 molCaCO3 ha−1 yr−1. Data obtained from flow-through dissolution experiments suggest that at near neutral pH, granule geometric surface areanormalised dissolution rates are similar to those for other biogenic and inorganic calcium carbonate. Fits of the data to the dissolution relationship r = k(1 − ˝)n where r = dissolution rate, k = a rate constant, ˝ = relative saturation and n = the reaction order gave values of k = 1.72 × 10−10 mol cm−2 s−1 and n = 1.8 for the geometric surface area-normalised rates and k = 3.51 × 10−13 mol cm−2 s−1 and n = 1.8 for the BET surface area-normalised rates. In 196 day leaching column experiments trends in granule dissolution rate referenced to soil chemistry corresponded to predictions made by the SLIM model for dissolution of limestone in soil. If soil solution approaches saturation with respect to calcium carbonate granule dissolution will slow or even stop and granules be preserved indefinitely. Granules have the potential to be a small but significant component of the biogeochemical cycling of C and Ca in soil.

π-dimerization of pleiadiene radical cations at low temperatures revealed by UV–vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[ c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293–263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPRsilent π-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; logεmax=4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF6 − salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol−1 (DFT B3LYP) [37.64 kcal mol−1 (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TDDFT- calculated UV–vis spectra of the PF6 − salt of the pleiadiene dimer dication, considering solvent (THF) effects.

Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Haldane's Mackindergarten: a radical experiment in British military education

This article critically evaluates a course that was conceived and run at the LSE by Sir Halford Mackinder for officers of the Britsh Army between 1907 and 1932.There is an examination of the nature of the syllabus,the aims and objectives of this course.An explanation is also given as to why the army cut it seven years before the outbreak of the Second World War.

Color adjectives and radical contextualism

Radical contextualists have observed that the content of what is said by the utterance of a sentence is shaped in far-reaching ways by the context of utterance. And they have argued that the ways in which the content of what is said is shaped by context cannot be explained by semantic theory. A striking number of the examples that radical contextualists use to support their view involve sentences containing color adjectives (“red”, “green”, etc.). In this paper, I show how the most sophisticated analysis of color adjectives within the explanatory framework of compositional truth conditional semantics—recently developed by Kennedy and McNally (Synthese 174(1):79–98 2010)—needs to be modified to handle the full range of contextual variation displayed by color adjectives.

The paradox of nationalism: the common denominator of radical right and radical left euroscepticism

What can explain the strong euroscepticism of radical parties of both the right and the left? This article argues that the answer lies in the paradoxical role of nationalism as a central element in both party families, motivating opposition towards European integration. Conventionally, the link between nationalism and euroscepticism is understood solely as a prerogative of radical right-wing parties, whereas radical left-wing euroscepticism is associated with opposition to the neoliberal character of the European Union.This article contests this view. It argues that nationalism cuts across party lines and constitutes the common denominator of both radical right-wing and radical left-wing euroscepticism. It adopts a mixed-methods approach, combining intensive case study analysis with quantitative analysis of party manifestos. First, it traces the link between nationalism and euroscepticism in Greece and France in order to demonstrate the internal validity of the argument. It then undertakes a cross-country statistical estimation to assess the external validity of the argument and its generalisability across Europe.

The civic zeitgeist: nationalism and liberal values in the European radical right

This article examines the relationship between nationalism and liberal values, and more specifically the redefinition of boundaries between national communities and others in the rhetoric of radical right parties in Europe. The aim is to examine the tension between radical right party discourse and the increasing need to shape this discourse in liberal terms. We argue that the radical right parties that successfully operate within the democratic system tend to be those best able to tailor their discourse to the liberal and civic characteristics of national identity so as to present themselves and their ideologies as the true authentic defenders of the nation's unique reputation for democracy, diversity and tolerance. Comparing the success of a number of European radical right parties ranging from the most electorally successful SVP to the more mixed BNP, FN and NPD, we show that the parties that effectively deploy the symbolic resources of national identity through a predominantly voluntaristic prism tend to be the ones that fare better within their respective political systems. In doing so, we challenge the conventional view in the study of nationalism which expects civic values to shield countries from radicalism and extremism.

Complexes of NiX2 (X=Cl− and NO3−) with a NNO donor Schiff base: anion dependent structural variations and spectroscopic behaviour

Two new nickel(11) complexes, [NiLL'(H2O)(2)Cl] (1) and [{NiLL'(H2O)](2)(mu-H)]NO3·H2O(2), have been synthesized using a tridentate Schiff base ligand, HL, 2-[(2-dimethylamino-ethylimino)-methyl]-phenol, along with Cl- or NO3(-) as an anionic co-ligand or counter anion (where L'H = salicylaldehyde). Both complexes have been characterized by X-ray crystallography. The structural analyses reveal that complex 1 is mononuclear whereas 2 is a hydrogen-bridged dinuclear complex. The Ni(II) ions possess a distorted octahedral geometry in both structures. Both complexes show negative solvatochromic behaviour with increasing donor number (DN) of the solvent. In more coordinating solvents, like DMSO or methanol, the colour of the solutions is green, whereas in less coordinating solvents, like dichloromethane (DCM) or acetonitrile, it is red.

Radical Conservatism

In 1938, Yugoslav sculptor Oscar Nemon arrived in Britain, having fled the Nazi invasion of Brussels, where he was living with Magritte. He was part of the European avant-garde that came to the UK as a refugee. Shortly thereafter, Nemon proposed a bold architectural plan to construct a temple of universal ethics in London and was in correspondence over this with central figures in Britain. After the war, he became know for his portrayal of figures like Churchil, culminating in a bust of Margaret Thatcher that is currently at the Tory HQ. Shown at Castlefield Gallery in 2013-2014, Radical Conservatism was an exhibition that explored the space between these two moments and asked whether these two terms are really antithetical. In the British context in particular, where the European avant-garde never really took hold, a kind of reactionary modernism has always defined a culture wary of revolution. But today more than ever, with the left increasingly holding on to the past of the welfare state as an ideal, and the right quietly revolutionising our world through neoliberal reforms, the paradigms of radicalism and conservatism need to be redefined. Can conservatism be seen as a radical position in itself? If art is defined by a movement towards the new - could 'holding on to the past' stubbornly be seen as a critical position, now that neo-liberalism has forced a far more radical shift in politics than the left has managed in a long time? Curated by Pil and Galia Kollectiv, featuring work by Chris Evans, IRWIN, Pil and Galia Kollectiv, Joseph Lewis, Patrick Moran, Oscar Nemon and Public Movement and a symposium with contributions from Professor Alun Rowlands and Robert Garnett.

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine ando-hydroxyacetophenone in NiII and CuII Complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks.