Made available in DSpace on 2014-06-11T19:28:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-01-09Bitstream added on 2014-06-13T20:58:21Z : No. of bitstreams: 1 costa_rss_me_jabo.pdf: 196990 bytes, checksum: c75125a9aa5fdd7fdef314a312cabaed (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O zinco é um micronutriente considerado limitante à produção do milho no Brasil, sendo a sua deficiência muito comum em todas as regiões do país. Com o objetivo de avaliar os efeitos de doses e fontes de Zn nas concentrações do micronutriente no solo, na planta e na produção de matéria seca da parte aérea do milho, foi conduzido um experimento em casa de vegetação, empregando-se amostra de um Latossolo Vermelho textura média. O delineamento experimental foi inteiramente casualizado, com três repetições, segundo um arranjo fatorial 6 x 3 (seis doses de Zn e três fontes). Foram empregadas as seguintes doses de Zn: 0; 0,5; 1; 2; 4 e 6 mg kg-1, utilizando-se as fontes: Zn-EDTA, Zn-lignosulfonato (Zn-LS) e sulfato de zinco. Verificou-se que a aplicação de Zn, independentemente da fonte considerada, aumentou significativamente a produção de matéria seca da parte aérea de milho e as concentrações do micronutriente no solo e na planta. A fonte Zn-LS proporcionou concentrações de Zn no solo e na planta significativamente superiores, particularmente em relação à fonte inorgânica. As fontes de Zn apresentaram um comportamento semelhante em termos de produção de matéria seca. Os níveis críticos de Zn no solo e na parte aérea da planta foram respectivamente, 0,9 e 16 mg kg-1. / The zinc is a micronutrient that limits the production of the maize in Brazil, being its very common deficiency in all the regions of the country. With the objective of evaluating the effect of the zinc rates in micronutrients concentration in soil, in plants and maize shoot dry matter production, an experiment in pots containing Haplustox (Latossolo Vermelho). It was used a complete randomized design, with three replications of treatments, in a factorial arrangement 6 x 3 (six rates of zinc and three sources). It was used following rates of zinc: 0; 0.5; 1; 2; 4 e 6 mg kg-1, and sources: Zn-EDTA, Zn-lignosulfonate (Zn-LS) and zinc sulfate. It was observed zinc application, own the sources, increased corn shoot dry matter and the micronutrient concentration in soil and plant. The source Zn-LS provided more Zn concentration in soil and plant than inorganic source. The zinc sources showed the same performance in dry matter production. The Zn level critic in soil and plant were respectively 0.9 mg kg-1 and 16 mg kg-1.

Orientador: Edson Luiz Mendes Coutinho / Banca: Salatier Buzetti / Banca: Mara Cristina Pessôa da Cruz / Resumo: O zinco é um micronutriente considerado limitante à produção do milho no Brasil, sendo a sua deficiência muito comum em todas as regiões do país. Com o objetivo de avaliar os efeitos de doses e fontes de Zn nas concentrações do micronutriente no solo, na planta e na produção de matéria seca da parte aérea do milho, foi conduzido um experimento em casa de vegetação, empregando-se amostra de um Latossolo Vermelho textura média. O delineamento experimental foi inteiramente casualizado, com três repetições, segundo um arranjo fatorial 6 x 3 (seis doses de Zn e três fontes). Foram empregadas as seguintes doses de Zn: 0; 0,5; 1; 2; 4 e 6 mg kg-1, utilizando-se as fontes: Zn-EDTA, Zn-lignosulfonato (Zn-LS) e sulfato de zinco. Verificou-se que a aplicação de Zn, independentemente da fonte considerada, aumentou significativamente a produção de matéria seca da parte aérea de milho e as concentrações do micronutriente no solo e na planta. A fonte Zn-LS proporcionou concentrações de Zn no solo e na planta significativamente superiores, particularmente em relação à fonte inorgânica. As fontes de Zn apresentaram um comportamento semelhante em termos de produção de matéria seca. Os níveis críticos de Zn no solo e na parte aérea da planta foram respectivamente, 0,9 e 16 mg kg-1. / Abstract: The zinc is a micronutrient that limits the production of the maize in Brazil, being its very common deficiency in all the regions of the country. With the objective of evaluating the effect of the zinc rates in micronutrients concentration in soil, in plants and maize shoot dry matter production, an experiment in pots containing Haplustox (Latossolo Vermelho). It was used a complete randomized design, with three replications of treatments, in a factorial arrangement 6 x 3 (six rates of zinc and three sources). It was used following rates of zinc: 0; 0.5; 1; 2; 4 e 6 mg kg-1, and sources: Zn-EDTA, Zn-lignosulfonate (Zn-LS) and zinc sulfate. It was observed zinc application, own the sources, increased corn shoot dry matter and the micronutrient concentration in soil and plant. The source Zn-LS provided more Zn concentration in soil and plant than inorganic source. The zinc sources showed the same performance in dry matter production. The Zn level critic in soil and plant were respectively 0.9 mg kg-1 and 16 mg kg-1. / Mestre

The worldwide occurrence of sites contaminated with toxic metals and the associated high costs of remediating them using chemical and mechanical methods have led to calls to develop inexpensive and sustainable approaches based on the use of plants that naturally accumulate large amounts of metals in their tissues. The ability of plants to remediate metals has been rigorously studied and some species have been identified as excellent phytoremediators. However, the growth of phytoremediators is often retarded under high soil metal concentrations, rendering them ineffective. Meanwhile, some plants do not have remediating abilities but are capable of growing in contaminated environments with little or no sign of stress. Despite the volume of research dedicated to the screening and evaluation of phytoremediators, major questions remain about why some plants survive but do not remediate while the growth of phytoremediators is mostly hindered. The growth and metal-remediating efficiency of plants exposed to toxic concentrations of metals can be enhanced by inoculating phytoremediating plants with certain bacteria but the mechanisms behind this process remain unclear. Furthermore, the use of leguminous plants to improve the growth of a target plant under a mixed planting system has long been recognised as an effective yield-enhancing cropping system. However, the possibility of a non-remediating but tolerant leguminous plant conferring metal tolerance to a phytoremediator has not been explored. This thesis reports results from repeated glasshouse and lab-based growth experiments on the phytoremediating plant Brassica juncea exposed to 400 – 600 mg Zn kg-1. The aim was to investigate the abilities of two plant growth promoting bacteria (PGPB) species Pseudomonas brassicacearum and Rhizobium leguminosarum, and a leguminous plant Vicia sativa to promote B. juncea growth and enhance remediation of Zn-contaminated soil. B. juncea plant roots were analysed using synchrotron based micro-focus X-ray Fluorescence (μXRF) imaging and X-ray Absorption Near Edge Structure (μXANES) analysis to probe Zn speciation. P. brassicacearum exhibited the poorest plant growth promoting ability, while R. leguminosarum alone and in combination with P. brassicacearum significantly enhanced B. juncea growth and Zn bioaccumulation. X-ray Absorption Spectroscopy (XAS) analysis showed that reduced plant growth was due to root accumulation of Zn as Zn sulphate, Zn oxalate and Zn polygalacturonic acids. The better growth and increased metal accumulation observed in plants inoculated with R. leguminosarum and its combination with P. brassicacearum was attributed to root storage of Zn in the chelated forms of Zn phytate and Zn cysteine. A subcellular analysis of plant root also showed that the PGPB enhanced tolerance to Zn contamination by enhancing epidermal Zn compartmentalisation depending on the nature of root colonization, and induced changes in Zn speciation to less toxic Zn species in the epidermis and endodermis of plant root. The thesis therefore identifies enhanced Zn compartmentalization at the root epidermis and bacterial mediated changes in Zn toxicity through changes in Zn speciation as key complimentary mechanisms of plant growth promotion and enhanced Zn accumulation in plants by PGPB. Further experiments investigating alternative phytoremediation strategies showed that the use of the leguminous plant V. sativa in a mixed planting system with B. juncea plants completely out performed the effects of bacteria in promoting the growth and remediation potential of B. juncea under Zn contamination. By combining PGPB with mixed planting, B. juncea recovered full growth while also achieving maximum phytoremediation efficiency. The novel legume assistedmicrobial phytoremediation method that is reported in this thesis is the first to demonstrate complete plant growth recovery in plants exposed to 400 – 450 mg kg-1 soil Zn contamination for 5 weeks. Survival of V. sativa was attributed to its root storage of Zn in the chelated forms of Zn histidine and cysteine whereas in the roots of stunted B. juncea plants the majority of Zn was present as Zn oxalate and toxic Zn sulphate. Although the use of natural and synthetic chelates has been reported to enhance phytoremediation, this thesis recommends a legume-assisted-microbialphytoremediation system as a more sustainable method for Zn bioremediation.

Neste trabalho, foram depositadas sobre lâminas de silício camadas de zeólitos cristalinos, formados por cadeias de átomos de zinco e bases conjugadas do imidazol (ZIF: Zeolitic Imidazolate Framework), com o objetivo de avaliar os processos de adsorção e absorção do CO2 e aplicar essas camadas como pré-concentradores para a detecção de CO2. Para a deposição das camadas ZIF através dos processos Spinning e casting, foi proposta uma solução química alternativa que emprega etanol como solvente em vez de metanol como reportado na literatura, a fim de proporcionar um processo menos tóxico ao ser humano e viabilizar o armazenamento de CO2 para aplicações envolvendo não apenas a sua detecção mas também a sua remoção do ambiente. As camadas ZIF foram depositadas utilizando uma solução obtida a partir da mistura de nitrato de zinco (4,3g) e 2-metilimidazol (9,7g) em etanol com diversas diluições com a finalidade de variar o pH na faixa de 7,2 a 8,2. Como resultado, verificou-se que as camadas obtidas apresentaram estrutura cristalina ZIF-8 ou ZIF-90 apenas na situação de pH próximo de 7. Além disso, as camadas depositadas através da técnica Spinning apresentaram baixa aderência sobre lâminas de silício e não foi possível depositar camadas com espessuras na faixa de micrômetros. Por outro lado, camadas repetitivas com aproximadamente 7, 5µm de espessura foram depositadas nas lâminas de silício através do processo casting em solução de pH = 7,2 (50ml). Após o recozimento dessas camadas na temperatura de 150 ºC por 48h em ambiente de nitrogênio ultrapuro, obtiveram-se distribuições repetitivas de nanocristais com tamanhos na faixa de 5 a 400nm e estrutura cristalina tipo ZIF-90. Das medidas de espectroscopia IR nas camadas de ZIF-90, observou-se que a banda localizada em 2337cm-1 intensifica com o aumento da pressão do CO2 e com o tempo em que a pressão é mantida. Além da banda em 2337cm-1, foi observada uma segunda banda em 2360cm-1, indicando dois diferentes tipos de resposta: (i) a banda em 2337cm-1 foi associada a uma porção substancial de moléculas de CO2 absorvidas dentro da camada junto aos contornos dos nanocristais ou dentro da sua estrutura cristalina, e (ii) a banda em 2360cm-1 foi atribuída à porção de moléculas de CO2 adsorvidas na superfície. Além disso, se o tempo de exposição da camada de ZIF-90 ao CO2, na pressão atmosférica for de pelomenos 2h, atinge-se sensibilidade de 100ppm ao CO2, considerando a leitura mínima de absorbância como sendo igual a 0,02 para 0,5 l/min de CO2 fluindo sobre a amostra. / In this work, layers of crystalline zeolites formed by chains of zinc atoms and conjugate bases of the imidazole (ZIF: zeolitic Imidazolate Framework) were deposited to evaluate the desorption and absorption of CO2 and apply these layers as pre-concentrators for CO2 detection. For the deposition of ZIF layers by means of spinning or casting, it was proposed an alternative chemical solution which employs ethanol as solvent instead of methanol, as reported in the literature, to provide a less toxic process to humans and allow one the CO2 storage applications involving not just detection but also its removal from the environment. The ZIF layers were deposited using a solution prepared from a mixture of zinc nitrate (4.3g) and 2-methylimidazole (9.7g) with several dilutions in ethanol to vary the pH in the range of 7.2 to 8.2. As a result, the crystalline structure of the layers was ZIF-8 or ZIF-90 only for pH next to 7. Furthermore, the layers deposited by spinning showed low adhesion to the silicon wafers and it was not possible to deposit layers for thickness in the micrometer range. Moreover, repetitive layers of approximately 7.5µm in thickness were deposited on the silicon wafers by casting for pH = 7.2 (50ml). After annealing these layers at a temperature of 150 ºC for 48h in ultra-pure nitrogen, it was obtained repetitive nanocrystals with size distributions in the range of 5 to 400 nm having a ZIF-90 crystal structure. From infrared (IR) measurements of the ZIF-90 layers, it was observed a band located at 2337cm-1 that increases with the increase of the CO2 pressure and with the exposure time to this pressure. In addition to the band at 2337cm-1, it was observed a second band at 2360cm-1 indicating two different responses: (i) the band at 2337cm-1 is related to a substantial portion of the CO2 molecules absorbed into the layer along the contours of the nanocrystals or within the crystal structure and (ii) the band at 2360cm-1 is related to the portion of CO2 molecules adsorbed on the surface. Also, if the ZIF-90 layer is exposed to CO2 at atmospheric pressure for at least 2h, a 100ppm sensitivity to CO2 is achieved considering the minimum absorbance as being 0.02 when 0.5 l/min of CO2 is flowing on the sample.

Neste trabalho, foram depositadas sobre lâminas de silício camadas de zeólitos cristalinos, formados por cadeias de átomos de zinco e bases conjugadas do imidazol (ZIF: Zeolitic Imidazolate Framework), com o objetivo de avaliar os processos de adsorção e absorção do CO2 e aplicar essas camadas como pré-concentradores para a detecção de CO2. Para a deposição das camadas ZIF através dos processos Spinning e casting, foi proposta uma solução química alternativa que emprega etanol como solvente em vez de metanol como reportado na literatura, a fim de proporcionar um processo menos tóxico ao ser humano e viabilizar o armazenamento de CO2 para aplicações envolvendo não apenas a sua detecção mas também a sua remoção do ambiente. As camadas ZIF foram depositadas utilizando uma solução obtida a partir da mistura de nitrato de zinco (4,3g) e 2-metilimidazol (9,7g) em etanol com diversas diluições com a finalidade de variar o pH na faixa de 7,2 a 8,2. Como resultado, verificou-se que as camadas obtidas apresentaram estrutura cristalina ZIF-8 ou ZIF-90 apenas na situação de pH próximo de 7. Além disso, as camadas depositadas através da técnica Spinning apresentaram baixa aderência sobre lâminas de silício e não foi possível depositar camadas com espessuras na faixa de micrômetros. Por outro lado, camadas repetitivas com aproximadamente 7, 5µm de espessura foram depositadas nas lâminas de silício através do processo casting em solução de pH = 7,2 (50ml). Após o recozimento dessas camadas na temperatura de 150 ºC por 48h em ambiente de nitrogênio ultrapuro, obtiveram-se distribuições repetitivas de nanocristais com tamanhos na faixa de 5 a 400nm e estrutura cristalina tipo ZIF-90. Das medidas de espectroscopia IR nas camadas de ZIF-90, observou-se que a banda localizada em 2337cm-1 intensifica com o aumento da pressão do CO2 e com o tempo em que a pressão é mantida. Além da banda em 2337cm-1, foi observada uma segunda banda em 2360cm-1, indicando dois diferentes tipos de resposta: (i) a banda em 2337cm-1 foi associada a uma porção substancial de moléculas de CO2 absorvidas dentro da camada junto aos contornos dos nanocristais ou dentro da sua estrutura cristalina, e (ii) a banda em 2360cm-1 foi atribuída à porção de moléculas de CO2 adsorvidas na superfície. Além disso, se o tempo de exposição da camada de ZIF-90 ao CO2, na pressão atmosférica for de pelomenos 2h, atinge-se sensibilidade de 100ppm ao CO2, considerando a leitura mínima de absorbância como sendo igual a 0,02 para 0,5 l/min de CO2 fluindo sobre a amostra. / In this work, layers of crystalline zeolites formed by chains of zinc atoms and conjugate bases of the imidazole (ZIF: zeolitic Imidazolate Framework) were deposited to evaluate the desorption and absorption of CO2 and apply these layers as pre-concentrators for CO2 detection. For the deposition of ZIF layers by means of spinning or casting, it was proposed an alternative chemical solution which employs ethanol as solvent instead of methanol, as reported in the literature, to provide a less toxic process to humans and allow one the CO2 storage applications involving not just detection but also its removal from the environment. The ZIF layers were deposited using a solution prepared from a mixture of zinc nitrate (4.3g) and 2-methylimidazole (9.7g) with several dilutions in ethanol to vary the pH in the range of 7.2 to 8.2. As a result, the crystalline structure of the layers was ZIF-8 or ZIF-90 only for pH next to 7. Furthermore, the layers deposited by spinning showed low adhesion to the silicon wafers and it was not possible to deposit layers for thickness in the micrometer range. Moreover, repetitive layers of approximately 7.5µm in thickness were deposited on the silicon wafers by casting for pH = 7.2 (50ml). After annealing these layers at a temperature of 150 ºC for 48h in ultra-pure nitrogen, it was obtained repetitive nanocrystals with size distributions in the range of 5 to 400 nm having a ZIF-90 crystal structure. From infrared (IR) measurements of the ZIF-90 layers, it was observed a band located at 2337cm-1 that increases with the increase of the CO2 pressure and with the exposure time to this pressure. In addition to the band at 2337cm-1, it was observed a second band at 2360cm-1 indicating two different responses: (i) the band at 2337cm-1 is related to a substantial portion of the CO2 molecules absorbed into the layer along the contours of the nanocrystals or within the crystal structure and (ii) the band at 2360cm-1 is related to the portion of CO2 molecules adsorbed on the surface. Also, if the ZIF-90 layer is exposed to CO2 at atmospheric pressure for at least 2h, a 100ppm sensitivity to CO2 is achieved considering the minimum absorbance as being 0.02 when 0.5 l/min of CO2 is flowing on the sample.

Excessive metal deposition in soil is of major concern to the environment due to the toxicity of metals to animals and plants. Since metals do not degrade, reducing risk of exposure relies in either removing the metals from soil, or changing their speciation which leads to changes in bioavailability, mobility and toxicity. Plants have been shown to provide a cheap alternative to chemical methods for both removing and changing metal speciation, particularly when augmented with plant growth promoting bacteria. The focus of this thesis was to investigate whether the form (speciation) in which a metal contaminant is introduced to soil affects both plant health and the efficiency of metal remediation by the plant, using the well-known hyperaccumulator Brassica juncea (L.) Czern and zinc (Zn) as the metal contaminant. This study also examined the role of plant growth promoting bacteria in changing metal speciation, impact on metal toxicity and phytoremediation efficiency. Brassica juncea was grown in pots containing soil spiked with equal amounts (600 mg Zn kg-1) of soluble Zn (ZnSO4) and nanoparticulate ZnS and ZnO. Plant height, number of leaves, root length, plant biomass and chlorophyll content of Brassica juncea were used to assess Zn toxicity. Zn localisation and speciation in soil and plant tissues was studied using transmission electron microscopy (TEM), synchrotron micro-X-ray fluorescence elemental mapping (μXRF) and synchrotron X-ray absorption spectroscopy (XAS). Growth parameters showed that ZnSO4 was the most toxic form of Zn whilst ZnS and ZnO effects were not statistically different. These differences were linked to differences in Zn content in root and shoot biomass, which was higher in ZnSO4 treatments. Inoculation with Rhizobium leguminosarum and Pseudomonas brassicacearum enhanced plant growth, Zn concentration in plant biomass and translocation of Zn in all Zn treatments. XAS analysis showed that Zn speciation was altered in roots of plants inoculated with bacteria, with Zn cysteine as the most dominant form of Zn in all inoculated Zn treatments, suggesting a role for cysteine in ameliorating Zn toxicity. By also assessing Zn speciation changes across the soilrhizosphere- plant interface, this study established that Rhizobium leguminosarum modified Zn speciation at the rhizosphere. Through this thesis work, metal speciation is a major factor in determining the efficiency of metal phytoremediation and plant tolerance. Hence, this research provides useful information on Zn speciation which will contribute to effective implementation of Zn phytoremediation.

Fordonsindustrin strävar efter ständiga förbättringar på transmissionssystem inom exempelvis hållfasthet och viktminskning. För att reducera vikten på växellådshuset (VE15) har alternativ till det befintliga skruvförbandet granskats. Målet med examensarbetet var att välja två olika fogningsmetoder, en inom svetsning och en inom limning. De valda fogningsmetoderna jämfördes med det befintliga skruvförbandet utifrån bland annat viktminskningspotential och hållfasthet. Information inom svetsning, limning, skruvförband och aluminium införskaffades med hjälp av kvalificerade databaser, vetenskapliga artiklar samt rådfrågning av sakkunniga inom respektive område. Utifrån de valda fogningsmetoderna, friktionsomrörningssvetsning (FSW) och epoxi, idégenererades utformning av flänsen. Vid användning av FSW som fogningsmetod reducerades vikten på VE15 med 13,7 % och med epoxi var viktminskningen 25,5 %, i jämförelse med skruvförbandet. Då mekaniken i växellådan genererar krafter på flänsen är hållfasthetsegenskaper hos fogningsmetoderna viktiga. Epoxi, FSW och skruvförbandet klarar belastningarna med god marginal. Med avseende på bland annat hållfasthet, vikt och miljö/hälsopåverkan valdes FSW som potentiell ersättare av skruvförbandet på VE15. Valet utfördes med en konceptvägningsmatris.

Non-volatile memory is slower than DRAM (Dynamic Random Access Memory) but faster than HDD (Hard Disk Drive). In addition, compared to volatile memory, the non-volatile memory can retain stored information without power, and consume only low power. These characteristics show its popularity of flash memory built in portable devices. Currently the non-volatile memory applies the polysilicon and SONOS structure as floating gate, however, the new technologies of nanocrystal non-volatile memory are processed at high temperature. The manufacturing cost is rather high, so the process at lower temperature is very necessary. In this work, mixed zinc and silica amorphous layers are applied as floating gate to construct nano thin film non-volatile memory devices. The process does not need high temperature to form crystalline, and the defects in zinc oxide can be applied for charge storage. Supercritical carbon dioxide (SCCO2) treatment has been studied for the passivation of dielectric and reducing the activation energy. Using this low-temperature SCCD process ZnO nanocrystal can be formed, and the feasibility of fabricating nanocrystal NVMs device with low temperature SCCO2 is possible. The nonvolatile memory devices with Zn nano thin film embedded in MIS structure are performed. From C-V measurement, it is found that defects in SiO2 are repaired after 500¢J annealing. Because of the thermal diffusion, the storage layer SiO2/Zn-SiO2/SiO2 in device cannot be observed and the memory window disappears when the annealing temperature is higher than 700¢J. Therefore, the annealing process should be performed between 500¢J - 700¢J in making memory device. From DLTS analysis, a species with energy level of 0.6 eV is found in the as deposited Zn-SiO2 layer. After annealing in Ar, a new energy level 0.47 eV is found, and which shifts to energy level 0.85 eV after annealing in O2. In comparison to XPS results, traps of Zn-SiO2 exist before annealing, and after annealing in Ar, Zn-SiO2 transforms into Zn-O-Si. Traps of ZnO-SiO2 have been found after annealing in O2, which increases the memory effect with a 2 Volt memory window, so that more charges can be stored in the deep level traps of ZnO-SiO2 in the storage layer.

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Spin-polarized first-principles electronic structure and total energy calculations have been performed to better understand the magnetic properties of Co doped ZnO (ZnO:Co) with vacancies and Ga co-dopants. The paramagnetic state of ZnO:Co, in which Co ions lose their magnetic moments, has been found to be unstable. The total energy results show that acceptor-like Zn vacancies and donor-like Ga co-dopants render the anti-ferromagnetic (AFM) and ferromagnetic (FM) states to be more favorable, respectively. With O vacancies, ZnO:Co has been found to be in the weak FM state. These magnetic properties can be understood by the calculated O- and Zn-vacancies and Ga-co-dopant induced changes of the electronic structure, which suggest that AFM and FM Co-Co couplings are mediated by O 2p-Co majority (¡ô)-spin 3d hybridized states in the valence band of ZnO and O-vacancy-derived p states or Ga sp states in the ZnO band gap, respectively. For ZnO:Co with Zn vacancies (Ga co-dopants) the AFM (FM) coupling outweighs the FM (AFM) coupling and results in the AFM (FM) state, while for ZnO:Co with O vacancies, both the FM and AFM couplings are enhanced by similar degrees and result in the weak FM state. This study reveals a competition between FM and AFM couplings in ZnO:Co with vacancies and Ga co-dopants, the detailed balancing between which determines the magnetic properties of these materials.