Spatial ecology of food webs : herbivore-parasitoid communities on the pedunculate oak

Herbivorous insects, their host plants and natural enemies form the largest and most species-rich communities on earth. But what forces structure such communities? Do they represent random collections of species, or are they assembled by given rules? To address these questions, food webs offer excellent tools. As a result of their versatile information content, such webs have become the focus of intensive research over the last few decades. In this thesis, I study herbivore-parasitoid food webs from a new perspective: I construct multiple, quantitative food webs in a spatially explicit setting, at two different scales. Focusing on food webs consisting of specialist herbivores and their natural enemies on the pedunculate oak, Quercus robur, I examine consistency in food web structure across space and time, and how landscape context affects this structure. As an important methodological development, I use DNA barcoding to resolve potential cryptic species in the food webs, and to examine their effect on food web structure. I find that DNA barcoding changes our perception of species identity for as many as a third of the individuals, by reducing misidentifications and by resolving several cryptic species. In terms of the variation detected in food web structure, I find surprising consistency in both space and time. From a spatial perspective, landscape context leaves no detectable imprint on food web structure, while species richness declines significantly with decreasing connectivity. From a temporal perspective, food web structure remains predictable from year to year, despite considerable species turnover in local communities. The rate of such turnover varies between guilds and species within guilds. The factors best explaining these observations are abundant and common species, which have a quantitatively dominant imprint on overall structure, and suffer the lowest turnover. By contrast, rare species with little impact on food web structure exhibit the highest turnover rates. These patterns reveal important limitations of modern metrics of quantitative food web structure. While they accurately describe the overall topology of the web and its most significant interactions, they are disproportionately affected by species with given traits, and insensitive to the specific identity of species. As rare species have been shown to be important for food web stability, metrics depicting quantitative food web structure should then not be used as the sole descriptors of communities in a changing world. To detect and resolve the versatile imprint of global environmental change, one should rather use these metrics as one tool among several.

Charge-order driven multiferroic and magneto-dielectric properties of rare earth manganates

Charge-order driven magnetic ferroelectricity is shown to occur in several rare earth manganates of the general formula, Ln(1-x)A(x)MnO(3) (In = rare earth, A = alkaline earth). Charge-ordered manganates exhibit dielectric constant anomalies around the charge-ordering or the antiferromagnetic transition temperature. Magnetic fields have a marked effect on the dielectric properties of these compounds, indicating the presence of coupling between the magnetic and electrical order parameters. Magneto-dielectric properties are retained in small particles of the manganates. The observation of magneto-ferroelectricity in these manganates is in accordance with theoretical predictions.

Charge-order driven multiferroic and magneto-dielectric properties of rare earth manganates

Charge-order driven magnetic ferroelectricity is shown to occur in several rare earth manganates of the general formula, Ln(1-x)A(x)MnO(3) (In = rare earth, A = alkaline earth). Charge-ordered manganates exhibit dielectric constant anomalies around the charge-ordering or the antiferromagnetic transition temperature. Magnetic fields have a marked effect on the dielectric properties of these compounds, indicating the presence of coupling between the magnetic and electrical order parameters. Magneto-dielectric properties are retained in small particles of the manganates. The observation of magneto-ferroelectricity in these manganates is in accordance with theoretical predictions.

Piezoresistivity (with uniaxial strain) in nanocrystalline films of rare-earth manganites

We present a study of the piezoresistivity in nanostructured. polycrystalline films of La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 grown on oxidized Si (100) substrates. We have observed that the hole doped rare-earth manganites, which are well known for being colossal magnetoresistive (CMR) show change in its resistance under uniaxial strain even at room temperature. The piezoresistance was measured at room temperature by bending the Si cantilevers (on which the film is grown) in flexural mode both with compressive and tensile strain. The resistance of the film increases with tensile strain and decreases with compressive strain. A large gauge factor of 15-20 is seen in these films at room temperature.

Rare earth exchanged (Ce3+, La3+ and RE3+) H-Y zeolites as solid acid catalysts for the synthesis of linear alkyl benzenes

Rare earth exchanged H–Y zeolites were prepared by simple ion exchange methods at 353 K and have been characterized using different physicochemical techniques. A strong peak around 58 ppm in the 27Al{1H} MAS NMR spectra of these zeolites suggests a tetrahedral coordination for the framework aluminium. Small peak at or near 0 ppm is due to hexa-coordinated extra-framework aluminium and a shoulder peak near 30 ppm is a penta-coordinated aluminium species; [Al(OH)4]−. The vapor-phase benzene alkylation with 1-decene and 1-dodecene was investigated with these catalytic systems. Under the reaction conditions of 448 K, benzene/olefin molar ratio of 20 and time on stream 3 h, the most efficient catalyst was CeH–Y which showed more than 70% of olefin conversion with 48.5% 2-phenyldecane and 46.8%, 2-phenyldodecane selectivities with 1-decene and 1-dodecene respectively.

Crystal growth, transport and magnetic properties of rare-earth manganite Pr1-xPbxMnO3

Crystal growth, electrical and magnetic properties are reported for mixed valence manganite Pr1-xPbxMnO3 (x = 0.2, 0.23, and 0.3). The crystals with x = 0.2 and 0.23 are ferromagnetic and insulating, whereas that with x = 0.3 is ferromagnetic below 200 K and shows an insulator-metal transition at 235 K. This composition shows a magnetoresistance of 90% in a field of 5 T. In the paramagnetic region, the temperature dependence of magnetic susceptibility of the crystals follows a Curie-Weiss behavior. The thermal evolution of magnetization in the ferromagnetic phase varies as T-3/2, in accordance with Bloch's law. The spin-stiffness constant D obtained from the Bloch constant is found to increase linearly with x. The magnetization does not reach complete saturation upto a field of 5 T. A possible contribution of the Pr spins to the total magnetic moment is discussed.

Rare-earth chromium citrates as precursors for rare-earth chromites: lanthanum biscitrato chromium(III) dihydrate, La[Cr(C6H5O7)2]·2H

The thermal decomposition of lanthanum biscitrato chromium(III) dihydrate has been studied in static air and dynamic argon atmospheres. The complex decomposes in four steps: dehydration, decomposition of the citrate to an intermediate oxycarbonate, formation of LaCrO4(V) from oxycarbonate, and finally decomposition of LaCrO4(V) to LaCrO3. Formation of LaCrCrO4(V) requires the presence of oxygen The decomposition behaviour of a mechanical mixture of lanthanum citrate hydrate and chromium citrate hydrate was compared with that of the citrato complex. Both the starting material and the intermediates were characterized by X-ray diffraction, IR electronic and ESR spectroscopy, surface area and magnetic susceptibility measurements, as well as by chemical analysis. A scheme is proposed for the decomposition of lanthanum biscitrato chromium(III) dihydrate in air. LaCrO3 can be obtained at temperatures as low as 875 K by isothermal decomposition of the complex.

Investigation of novel cuprates of the TlCa1-xLnxSr2Cu2O7- δ (Ln=rare earth) series showing electron- or hole-superconductivity depending on the composition

Superconductivity in cuprates of the general formula TlCa1-xLnxSr2Cu2O7+ delta has been investigated as a function of Ln and x. Compositions with 0.250.25. Thus, these cuprates exhibit a composition-dependent electron- or hole-superconductivity. In the normal state, most of the members of the series traverse compositionally determined metal-insulator transitions. High-energy spectroscopies show the presence of Cu in the 1+ and 2+ states. The Raman frequency around 525 cm-1 characteristic of the Tl-O2-Cu linkage is sensitive to both Ln and x, indicating a possible involvement in the mechanism of superconductivity.

A series of metallic oxides of the formula La3LnBaCu5O13+δ (Ln = rare earth or Y)

Oxides of the formula La3LnBaCu5O13+δ (Ln = Nd, Sm, Gd, Dy, or Y) exhibiting metallic resistivity have been prepared and characterized. In the case of yttrium, a composition close to La2Y2BaCu5O13+δ, which is also metallic, could be prepared.

Towards a green synthesis of LAB's: Effect of rare earth metal ions on the benzene alkylation with 1-dodecene over NaFAU-Y zeolites

Chemically modified microporous materials can be prepared as robust catalysts suitable for application in vapor phase processes such as Friedel-Crafts alkylation. In the present paper we have investigated the use of rare earth metal (Ce3+, La3+, RE3+, and Sm3+) exchanged Na-Y zeolites as catalysts for the alkylation of benzene with long chain linear 1-olefin; 1-dodecene. Thermodesorption studies of 2,6-dimethylpyridine adsorbed catalysts (in the temperature range 573 to 873 K) show that the rare earth zeolites are highly Bronsted acidic in nature. A perfect correlation between catalyst selectivity towards the desired product (2-phenyldodecane) and Bronsted acid sites amount has been observed. (c) 2006 Springer Science + Business Media, Inc.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Luonnonhoitopellot maatalousympäristön luonnon monimuotoisuuden edistämisessä

Luonnonhoitopellot lisättiin uutena vapaaehtoisena toimenpiteenä maatalouden ympäristötukeen vuonna 2009. Luonnonhoitopeltoihin kuuluvat monivuotiset nurmipellot sekä niitty-, riista- ja maisemakasveilla kylvetyt pellot. Toimenpiteen avulla pyritään suojelemaan ja lisäämään maatalousympäristön luonnon monimuotoisuutta sekä muun muassa vähentämään maatalouden ravinnehuuhtoumia. Vuonna 2010 luonnonhoitopeltoja oli yli seitsemän prosenttia Suomen viljelyalasta. Luonnonhoitopeltojen ympäristövaikutusten arvioiminen ja toimenpiteen kehittäminen on tärkeää, jotta toimenpiteeseen käytettävät varat eivät valu hukkaan. Tämän tutkimuksen tavoitteena oli selvittää, millainen merkitys luonnonhoitopelloilla on maatalousympäristön monimuotoisuuden kannalta; millaiset luonnonhoitopellot ovat monimuotoisuuden kannalta arvokkaimpia; ja kuinka toimenpidettä kannattaa kehittää. Kysymyksiin pyrittiin vastaamaan tutkimalla putkilokasvilajistoa, -lajirikkautta ja kasvillisuuden rakennetta erilaisilla luonnonhoitopelloilla, sekä vertaamalla luonnonhoitopeltojen kasvillisuutta pientareiden ja niittyjen kasvillisuuteen. Maastotyö luonnonhoitopelloilla tehtiin kesällä 2010 Uudenmaan ja Pohjois-Pohjanmaan ELY-keskusalueilla. Lisäksi tutkimuslohkoista kerättiin tietoja viljelijäkyselyn kautta. Niittypellot osoittautuivat tutkimuksessa lajirikkaimmaksi luonnonhoitopeltotyypiksi, mikä selittynee lähinnä sillä, että ne kylvetään heikosti kilpailukykyisellä siemenseoksella. Nurmi- ja niittypelloilla lohkon viljavuus korreloi negatiivisesti lajirikkauden kanssa. Lajikoostumukseltaan kaikki luonnonhoitopellot eroavat toisistaan sekä maatalousympäristön puoliluonnontilaisista elinympäristöistä, ja lisäävät siten monimuotoisuutta maisematasolla. Luonnonhoitopeltojen lajisto ei ole kuitenkaan suojelun kannalta erityisen arvokasta. Toimenpiteen maatalousympäristöä rikastuttavaa vaikutusta vähentää, että tällä hetkellä valtaosa luonnonhoitopelloista on monivuotisia nurmipeltoja. Luonnonhoitopeltojen siemenseoksia kehittämällä, perustamis- ja hoitomenetelmiä tutkimalla ja neuvontaan panostamalla voidaan lisätä luonnonhoitopeltojen arvoa niin luonnon, viljelijän kuin yhteiskunnankin kannalta.