Inland waters including streams, rivers, reservoirs and lakes are regarded as a significant site of Organic Carbon (OC) cycling, and greenhouse gas production. As a result, there has been significant recent interest in the rates and fate of fluvial carbon exported from organic soils, such as peatlands. Additionally, peatlands can be subject to substantial degradation resulting in high rates of fluvial OC export, and this has led to efforts to repair degraded peatlands through restoration programmes. As a consequence, the study of degraded areas is useful to quantify the upper values of carbon release, understand processes of transformation, and evaluate the success of restoration programmes. Importantly peatlands are also collection areas for drinking water, which has implications for treatment, and requires better understanding of carbon cycling upstream of treatment works, in headwater rivers, reservoirs and pipes. UK upland blanket peat catchments are a key location in which to consider global questions surrounding fluvial carbon export and transformations, as they are highly degraded, provide a source of drinking water supply, and are currently undergoing pioneering methods of landscape scale restoration. This thesis considers Kinder Scout, an area of highly degraded and gullied blanket peatland in the South Pennines, UK. Using analysis of water samples collected over several years in the Kinder reservoir catchment and plateau, this thesis presents three novel contributions to global questions concerning OC cycling and peatlands. Firstly it provides (to date), the only carbon budget for a reservoir in a peat dominated catchment with high Particulate Organic Carbon (POC) export, which demonstrates that reservoirs may be net sources of Dissolved Organic Carbon (DOC), with the implication that POC-DOC interactions are important OC transformation mechanism in degraded systems. Secondly through use of a unique integrated combination of methods, it considers changes in carbon flux and composition in both river, lake and pipe locations, providing detailed understanding of the relative roles of river reaches, reservoirs and supply pipes, in controlling fluvial carbon cycling in peatland systems, and upstream of water treatment works. An important implication here, is that rate and direction of change in water treatability varies through a catchment. Finally, it includes results from the first widespread monitoring of the catchment scale effects of a new method of peatland revegetation. This restoration approach is being applied at landscape scale and the findings here, are that despite fears to the contrary, it does not lead to short term increases in fluvial carbon loss, which is an important piece of evidence supporting practical conservation approaches in these systems. To further enhance this research, a combination of field and laboratory investigations into carbon transformation processes, and ongoing restoration mentoring should be undertaken.

Temperate mixed forests are complex ecosystems composed of multiple vegetation types with very different physiological characteristics which are distributed over the landscape. This dissertation investigates the influence of these mixed plant landscapes on eddy-covariance flux data, and in particular, uses an ecohydrological model to study the influence of climate variability and insect infestation on a mixed forest at the Harvard Forest Long Term Ecological Research site in Massachusetts. There are significant seasonal and interannual variabilities in the extent and the orientation of the footprints of a flux tower (EMS-tower) as the Harvard Forest. The Gross Primary Productivity (GPP) flux was found to be largely dependent on the vegetation density during the green-up and senescence periods, but not during the mature period. Half of the interannual anomalies in the mature period GPP flux can be explained by the variation in the proportion of coniferous evergreen needleleaf forest (ENF) in the footprint. Every 1% decrease of ENF resulted in the increase of the GPP flux by 20 gC m-2. The spatially-distributed process-based Regional Hydro-Ecological Simulation System (RHESSys) model was implemented in two headwater catchments at the Harvard Forest to simulate water and carbon cycles from 1992 to 2008. Results were evaluated using field measurements such as streamflow and the GPP and evapotranspiration (ET) fluxes at two flux towers. The simulated annual GPP flux of the deciduous forest showed strong and significant long-term increases, six times higher than the GPP flux of the coniferous forest, while the increase in ET flux of both forests was small yet significant. The Harvard Forest was infested by Hemlock Woolly Adelgid (HWA) between 2004 and 2008, and although there has not yet been a significant increase in the total annual mortality, the small stature stands have started to die off by 5.7%. The HWA infestation has already resulted in an increased streamflow in the catchment dominated by hemlock stands (44% in area). In 2014, the increased annual streamflow was estimated as 81 mm using the RHESSys model with an embedded representation of the HWA-induced loss of water conductivity (calibrated using the Hemlock tower ET flux).

To describe the diffusion of atoms in the crystal lattice of a metal, we use the statistical model, which was previously well tested for the description of thermionic emission [1]. Atoms in the crystal lattice of a metal are held by large attractive forces, therefore the potential energy of moving, i.e. diffusing atoms is greater than the potential energy of the atoms of the crystal lattice by the value of u — the activation energy of the diffusion process.

No description available.

O crescimento e o desenvolvimento de ecossistemas florestais são fortemente influenciados pelas flutuações do clima. Sendo assim, espera-se que florestas de eucalipto de rápido crescimento sejam amplamente afetadas pelas mudanças climáticas. A utilização de métodos que possibilitem a avaliação e comparação dos atributos funcionais do xilema das árvores sob a dinâmica dos ciclos biogeoquímicos são necessários, a fim de antecipar e mitigar as consequências das mudanças climáticas no funcionamento das plantações. A análise do crescimento, anatomia, microdensidade e propriedades hidráulicas do xilema podem trazer importantes conhecimentos sobre a fisiologia das árvores. A avaliação dessas propriedades, contudo, ocorre geralmente em algumas regiões do xilema do tronco, ou ramos, sendo sua avaliação ao longo de todo o histórico das árvores um desafio. Assim, a relação entre as propriedades e atributos funcionais das árvores com os ciclos da água e do carbono no nível do ecossistema ainda não está claro. Em março de 2008, instalou-se em área localizada próxima do município de Itatinga-SP, a torre de fluxo do Projeto EucFlux. O projeto tem como objetivo avaliar os fluxos de carbono e água (eddy covariance) ao longo do crescimento e desenvolvimento de árvores de eucalipto. Isso, permite avaliar as dinâmicas biogeoquímicas sobre o ecossistema florestal, buscando predizer sua produtividade sob diferentes condições climáticas. Em novembro de 2009, mudas de Eucalyptus grandis foram plantadas na área experimental de 90 ha, sendo avaliadas (diâmetro, altura, volume, etc.) até maio de 2018 (final da rotação). Com o corte das árvores, uma análise retrospectiva das propriedades e atributos funcionais do xilema do tronco de árvores de E. grandis foi realizada. Buscando compreender as relações dessas propriedades com as variações inter-intranuais das variáveis climáticas e ciclos do carbono e da água registrados pela torre de fluxo. Os métodos, resultados e avanços do presente estudo são descritos em dois capítulos. No Capítulo I, utilizou-se amostras do lenho de Eucalyptus grandis, Tectona grandis e Cedrela fissilis, para a descrição de um protocolo para obtenção de cortes histológicos longos e seus potenciais usos para avaliação de anéis de crescimento de árvores de eucalipto e espécies arbóreas tropicais, em uma abordagem conjunta de anatomia microscópica, perfis de microdensidade e anatomia quantitativa. Para o Capítulo II, avaliou-se árvores de E. grandis, seus anéis de crescimento (classes dominantes e codominantes), relacionando o crescimento radial e as propriedades do lenho do seu tronco (anatomia e microdensidade conforme capítulo I) com os ciclos biogeoquímicos (torre de fluxo, eddy covariance) em um período de 8 anos e em resolução inter-intranual. Como também a relação da formação do xilema com o crescimento em altura das árvores no mesmo período e resolução. Observou-se diferenças significativas entre o crescimento e as propriedades do lenho das três classes de dominância, onde as dominantes, seguidas pelas codominantes e dominadas, apresentaram maiores dimensões e densidade do lenho. As variáveis climáticas e fluxos de carbono e água apresentaram forte correlação com as propriedades e atributos funcionais do lenho, onde maior temperatura média e disponibilidade de água, resultaram em maior crescimento do tronco, menor densidade do lenho e vasos de maior diâmetro e, assim, maior condutividade potencial do xilema. A evapotranspiração do ecossistema apresentou correlação significativa com todas as variáveis estudadas, sendo forte indício das flutuações das variáveis climáticas e, assim, regulador da formação do xilema e funcionamento das árvores. Observou-se correlação entre os fluxos de carbono e crescimento, onde valores mais negativos de C (maior sequestro) resultaram em maior crescimento. O evento de estresse hídrico de 2014 teve forte efeito sobre os ciclos do carbono e da água, alterando assim, as propriedades do lenho das árvores. Ainda, o crescimento em altura teve forte correlação com as propriedades do lenho, onde maior altura resultou em vasos de maior dimensão e, assim, um sistema hidráulico com maior potencial de condução, contudo, com maior risco de cavitação e falha hidráulica. Os resultados integrados apontam o forte potencial da utilização de cortes histológicos longos para espécies tropicais, aprimorando a delimitação das camadas de crescimento anuais e permitindo a quantificação de variáveis anatômicas em conjunto com perfis de microdensidade, fundamentais para estudos fisiológicos das árvores. Assim, a relação das propriedades do lenho, com as flutuações das variáveis climáticas e ciclos do carbono e da água ao longo de todo o histórico de uma rotação de eucalipto em resolução inter-intranual tornou-se possível, indicando importantes novas possibilidades para os estudos de dendrocronologia e ciências florestais. / Growth and development of forest ecosystems are strongly influenced by climate fluctuations. Thus, fast-growing eucalyptus forests are expected to be largely affected by climate change. The use of methods that allow the evaluation and comparison of the functional traits of the tree xylem under the dynamics of the biogeochemical cycles are necessary in order to anticipate and mitigate the consequences of climate change on the functioning of plantations. The analysis of the growth, anatomy, microdensity and hydraulic properties of the xylem can bring important knowledge about the physiology of the trees. The evaluation of these properties, however, usually occurs in some regions of the trunk xylem, or branches, and their evaluation throughout the entire tree history is a challenge. Thus, the relationship between the properties and functional traits of trees with water and carbon cycles at the ecosystem level is still unclear. In March 2008, the flux tower of the EucFlux Project was installed in an area located near of Itatinga-SP. The project aims to evaluate the flux of carbon and water (eddy covariance) along the growth and development of eucalyptus trees. This allows to evaluate the biogeochemical dynamics on the forest ecosystem, seeking to predict its productivity under different climate conditions. In November 2009, seedlings of Eucalyptus grandis were planted in the experimental area of 90 ha, being evaluated (diameter, height, volume, etc.) until May 2018 (end of rotation). With the cut of the trees, a retrospective analysis of the properties and functional traits of the trunk xylem of E. grandis trees was performed. Seeking to understand the relationships of these properties with inter and intra annual variations of the climate variables and cycles of carbon and water, recorded by flux tower. The methods, results and advances of the present study are described in two chapters. In Chapter I, samples of Eucalyptus grandis, Tectona grandis and Cedrela fissilis wood, were used to describe a protocol for obtaining long histological sections and their potential uses for evaluation of growth rings of eucalyptus trees and tropical tree species, in a joint approach of microscopic anatomy, microdensity profiles and quantitative wood anatomy. For Chapter II, it was evaluated E. grandis trees, their growth rings (dominant and codominant classes), relating the radial growth and the wood properties of their trunk (anatomy and microdensity according to chapter I) to the biogeochemical cycles (flux tower, eddy covariance) over a period of 8 years in inter and intra annual resolution. As also, the relation of the xylem formation with the growth in height of the trees in the same period and resolution. Significant differences were observed between growth and wood properties of the three dominance classes, where dominant, followed by codominant and dominated, had larger wood dimensions and density. The climate variables and carbon and water fluxes showed a strong correlation with the properties and functional attributes of the wood, where higher mean temperature and water availability resulted in higher trunk growth, lower wood density and larger diameter vessels, greater potential conductivity of the xylem. The evapotranspiration of the ecosystem showed a significant correlation with all the studied variables, being a strong indication of the climate variables fluctuations and, therefore, regulator of xylem formation and tree functioning. There was a correlation between carbon fluxes and growth, where more negative values of C (higher sequestration) resulted in higher growth. The water stress event of 2014 had a strong effect on the carbon and water cycles, thus altering the wood properties of the trees. Also, the growth in height had a strong correlation with the properties of the wood, where higher height resulted in larger vessels and, thus, a hydraulic system with greater potential of conduction, however, with greater risk of cavitation and hydraulic failure. The integrated results point to the strong potential of using long histological sections for tropical species, improving the delimitation of the annual growth layers and allowing the quantification of anatomical variables together with microdensity profiles, fundamental for physiological studies of the trees. Thus, the relationship of wood properties with fluctuations in climate variables and cycles of carbon and water throughout the history of an inter-intranasal eucalyptus rotation became possible, indicating important new possibilities for the studies dendrochronology and forest sciences.

<p>Insekticidi novije generacije, neonikotinoidi, odlikuju se specifičnim načinom &nbsp;delovanja na&nbsp;nervni sistem insekata. Radi dobijanja &scaron;to brže i kvalitetnije informacije o izloženosti životne sredine&nbsp;ovim insekticidima i količinama njihovih ostataka u hrani potrebno je raspolagati odgovarajućim&nbsp;instrumentalnim metodama za njihovo određivanje. Razvijene su i optimizovane analitičke metode&nbsp;zasnovane na tečnoj hromatografiji za određivanje sedam odabranih neonikotinoida (dinotefurana,&nbsp;nitenpirama, tiametoksama, klotianidina, imidakloprida, acetamiprida &nbsp;i tiakloprida) u medu i likeru od&nbsp;meda. Ispitivana je mogućnost određivanja klotianidina pomoću tečne hromatografije visoke efikasnosti&nbsp;sa detektrorom od niza dioda (HPLC-DAD) primenom kombinacije tečno-tečne i ekstrakcije na čvrstoj&nbsp;fazi iz uzoraka meda. Na osnovu preliminarnih rezultata može se zaključiti da kori&scaron;ćenje &nbsp;faznih-čvrsto&nbsp;kolona u kombinaciji sa tečno-tečnom ekstrakcijom dihlormetanom rezultira prihvatljivim prinosom&nbsp;klotianidina u uzorcima meda pri koncentraciji od oko 0,5 &micro;g g^-1&nbsp;klotianidina. Radi dobijanja većih&nbsp;prinosa odabrana je disperzna tečno-tečna mikroekstrakcija (DLLME) kao tehnika pripreme uzoraka&nbsp;meda. Testirana je upotreba acetonitrila kao disperznog sredstva. Pored hloroforma, kori&scaron;ćen je i&nbsp;dihlormetan kao drugo ekstrakciono sredstvo, kako bi se &nbsp;uporedila efikasnost ekstrakcije. Zabeleženi su&nbsp;prinosi klotianidina od 69,7 i 68,3% &nbsp;u zavisnosti da li je kori&scaron;ćen hloroform, odnosno DHM kao rastvor&nbsp;za ekstrakciju. Može se zaključiti da je prinos ekstrakcije bio povoljniji pri odnosu 0,5 mL ACN i 2,0&nbsp;mL DHM. Prinosi su se kretali od 68,4% do 92,1%, &scaron;to je ukazalo da su parametri DLLME ekstrakcije optimalni. Kako bi se detaljnije ispitali ključni parametri DLLME tehnike, kori&scaron;ćena je metodologija povr&scaron;ine odziva (RSM), kao i detekcija na osetljivijem kuplovanom masenom detektoru (MS/MS). Optimizovani su HPLC-MS/MS &nbsp;parametri kako bi se obezbedilo zadovoljavajuće hromatografsko &nbsp;razdvajanje i niske granice detekcije (GD, 0,5&ndash;1,0 &mu;g kg^-1) i određivanja (GO, 1,0&ndash;2,5 &mu;g kg^-1) ispitivanih neonikotinoida u medu. Upotrebom centralno kompozitnog dizajna konstruisani su kvadratni modeli ispitivanih faktora: zapremine ekstrakcionog (DHM, 1,0&ndash;3,0 mL) i disperznog (ACN, 0,0&ndash;1,0 mL) sredstva, izračunati statistički parametri i optimizovan proces DLLME upotrebom <em>Derringer</em>-ove funkcije poželjnih odgovora. Upotrebom MMC i SC krivih u opsegu GO&ndash;100,0 &mu;g kg^-1&nbsp;ispitan je uticaj matriksa pri čemu zaključeno je da je najveći uticaj matriksa bio na odziv analitičkog signala nitenpirama, dinotefurana i klotianidina. Ispitani su prinosi odabranih neonikotinoida (R, 74,3&ndash;113,9%), kao i preciznost metode u uslovima ponovljivosti (RSD, 2,74&ndash; 11,8%) i intermedijerne reproduktivnosti (RSD, 6,64&ndash;16,2%). Brza (retenciona vremena 1,5&ndash;9,9 min) i osetljiva metoda, koja tro&scaron;i malu količinu rastvarača, primenjena je za ispitivanje 15 realnih uzoraka meda različitog cvetnog porekla. Rezultati su pokazali da ispitivani med nije sadržao ostatke ispitivanih neonikotinoida u koncentracijama iznad GD. Dalje istraživanje je bilo usmereno ka&nbsp; razvijanju i optimizaciji HPLC-DAD analitičke metode upotrebom DLLME i QuEChERS tehnika za &nbsp;pripremu uzoraka za određivanje 7 neonikotinoida u uzorcima meda. U ovom delu istraživanja optimizovani su i hromatografski parametri, upotrebom RSM sa Box-Behnken-ovim dizajnom i Derringer-ovom funkcijom poželjnih odgovora. Od &nbsp;ispitivanih neonikotinoida dinotefuran i imidakloprid su bili u najvećoj meri izloženi uticaju matriksa, bez obzira na proceduru pripreme uzoraka. Može se istaći da je uticaj matriksa na analitički signal dinotefurana bio izraženiji u slučaju MS/MS, apostrofirajući manju robusnost ove metode određivanja. Prinosi neonikotinoida su &nbsp;bili (R, 73,1&ndash;118,3%), preciznost u uslovima ponovljivosti (RSD, 3,28&ndash;10,40%) i intermedijerne reproduktivnosti (RSD, 6,45&ndash;17,70%), a granice detekcije (GD, 1,5&ndash;2,5 &micro;g kg^-1) i određivanja (GO, 5,0&ndash;10,0 &micro;g kg^-1). Metoda je primenjena za ispitivanje 7 neonikotinoida u 104 uzorkameda različitog cvetnog porekla sa &nbsp;teritorije Autonomne Pokrajine Vojvodine. Detektovano je prisustvo tiakloprida, imidakloprida i tiametoksama u količinama koje su bile ispod MDK RS i EU. Analizirani su uzorci likera od meda - medice. Upoređivane su dve tehnike pripreme uzoraka, DLLME i QuEChERS i primenjeni optimizovani hromatografski &nbsp;uslovi i MS/MS parametri. U slučaju nitenpirama, dinotefurana i tiametoksama uticaj matriksa bio je najizraženiji. Metoda je validovana određivanjem prinosa neonikotinoida (R, 69,2&ndash;113,4%), preciznosti u uslovima ponovljivosti (RSD, 3,21&ndash;12,81%) i intermedijerne reproduktivnosti (RSD, 9,11&ndash;16,63%), kao i granice detekcije (GD, 0,5&ndash;2,5 &micro;g kg^-1) i određivanja (GO, 1,0&ndash;10,0 &micro;g kg^-1). Analizom 10 komercijalno dostupnih likera od meda otkriveno je&nbsp;prisustvo klotianidina i tiakloprida, evčzokinot&scaron; z&nbsp; na neophodnost daljeg kontrolisanja ovog proizvoda na&nbsp;prisustvo neonikotinoida. Ispitana je mogućnost uklanjanja odabranih neonikotinoida (dinotefurana,&nbsp;klotianidina i tiakloprida) iz vodene sredine (reke Dunav). Ispitivanje efikasnosti 6 različitih vrsta&nbsp;uklanjanja odabranih neonikotinoida (u prisustvu prirodne insolacije u laboratorijskim uslovima, sa&nbsp;dodatkom H2O2, sa dodatkom MWCNT, sa dodatkom MWCN+H&nbsp;₂O₂, sa dodatkom Fe-MWCNT, sa dodatkom Fe-MWCNT+H₂O₂) vr&scaron;eno je upotrebom prethodno razvijene HPLC-MS/MS metode. Krive uklanjanja odabranih neonikotinoida, pokazale su da tokom 60 minuta pri prirodnoj insolaciji&nbsp; u laboratorijskim uslovima koncentracija smanjenje oko 25%. Analitički signal dinotefurana dobijen u prisustvu H₂O_2&nbsp;pod istim uslovima ukazuje na uklanjanje ciljnog analita od oko 40%, tiakloprida od oko 70%, a klotianidina u potpunosti. Testirana je adsorpcija ciljnog analita na vi&scaron;ezidnim ugljeničnim nanocevima (MWCNT). Ovim postupkom može da se ukloni oko 30% dinotefurana, oko 50% klotianidina i 60% tiakloprida. U kombinaciji sa H₂O_2&nbsp;, MWCNT pokazuju bolju sposobnost uklanjanja za 15&ndash;50% u zavisnosti od ispitivanog neonikotinoida. Upotreba Fe-MWCNT i njihova kombinacija sa H₂O₂ otvorila je mogućnost za dalja &nbsp;ispitivanja mehanizma uklanjanja. Ustanovljeno je nastajanje intermedijera kojima odgovaraju m/z od 117,5 i 140,6 u slučaju razgradnje dinotefurana u sistemima sa H₂O₂, MWCNT+H₂O₂, Fe-MWCNT+H₂O_2&nbsp;i klotianidina u sistemu Fe-MWCNT+H₂O₂.</p> / <p>Neonicotinoid insecticides, as one of the fastest growing new generation of insecticides, have&nbsp;contributed to a significant reduction of toxicity for the environment; therefore, monitoring and&nbsp;determination of trace levels of the neonicotinoids in honey are necessary and demands highly efficient,&nbsp;selective and sensitive analytical techniques. The objective of the present work was to develop a rapid,&nbsp;sensitive, optimized and accurate analytical method based on liquid chromatography for determining&nbsp;seven neonicotinoid insecticides, dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid,&nbsp;acetamiprid and thiacloprid in honey and honey liqueur samples. The possibility for determination of&nbsp;clothianidin in honey samples was investigated by HPLC with a diode array detector (HPLC-DAD).&nbsp;Based on preliminary results, it can be concluded that the use of a solid-phase column in combination&nbsp;with a liquid-liquid extraction with dichloromethane results in an acceptable recovery of clothianidin in&nbsp;the samples with a clothianidin concentration of about 0.5 &micro;g g^-1. After obtaining low recovery of&nbsp;clothianidin, dispersed liquid-liquid microextraction (DLLME) was selected as a technique for the&nbsp;preparation of honey samples.. The adequacy of acetonitrile as a dispersing agent was investigated.&nbsp;Besides the chloroform, a dichloromethane was used as a second extracting agent , in order to compare&nbsp;the relative efficiency of the extraction solvents. It can be concluded that the extraction recovery (68.4&ndash;92.1%) was more favorable with the use of 0.5 mL ACN and 2.0 mL DHM. Furthermore, LC-MS/MS&nbsp;parameters were optimized to unequivocally provide good chromatographic separation, low detection&nbsp;(LOD, 0.5&ndash;1.0 &mu;g L^&minus;1) and quantification (LOQ, 1.0&ndash;2.5 &mu;g L^&minus;1) limits for acetamiprid, clothianidin,&nbsp;thiamethoxam, imidacloprid, dinotefuran, thiacloprid and nitenpyram in honey samples. Using different&nbsp;<br />types (chloroform, dichloromethane) and volumes of extraction (1.0&ndash;3.0 mL) and dispersive&nbsp;(acetonitrile; 0.0&ndash;1.0 mL) solvent and by mathematical modeling it was possible to establish the optimal&nbsp;sample preparation procedure. Matrix-matched calibration and blank honey sample spiked in the&nbsp;<span style="font-size: 12px;">concentration range of LOQ&ndash;100.0 &mu;g kg</span>^{<span style="font-size: 12px;">&minus;1&nbsp;</span>}<span style="font-size: 12px;">were used to compensate the matrix effect and to fulfill the&nbsp;</span><span style="font-size: 12px;">requirements of SANCO/12495/2011 for the accuracy (R 74.3&ndash;113.9%) and precision (expressed in&nbsp;</span><span style="font-size: 12px;">terms of repeatability (RSD 2.74&ndash;11.8%) and within-laboratory reproducibility (RSDs &nbsp;6.64&ndash;16.2%)) of&nbsp;</span><span style="font-size: 12px;">the proposed method. The rapid (retention times 1.5&ndash;9.9 min), sensitive and low solvent consumption&nbsp;</span><span style="font-size: 12px;">procedure described in this work provides reliable, simultaneous, and quantitative method applicable for&nbsp;</span><span style="font-size: 12px;">the routine laboratory analysis of seven neonicotinoid residues in 15 real honey samples. Neonicotinoid &nbsp;</span><span style="font-size: 12px;">residues were not detected in any of the investigated samples. The objective of next study was to&nbsp;</span><span style="font-size: 12px;">develop and optimize HPLC-DAD analytical method with dispersive liquid-liquid microextraction&nbsp;</span><span style="font-size: 12px;">(DLLME) and QuEChERS sample preparation procedures for the simultaneously analysis of seven&nbsp;</span><span style="font-size: 12px;">neonicotinoids in honey samples. The liquid chromatographic conditions were optimized by response&nbsp;</span><span style="font-size: 12px;">surface methodology with <em>Box-Behnken</em> design and the global <em>Derringer</em>&acute;s desirability. The optimized&nbsp;</span><span style="font-size: 12px;">method was &nbsp;validated to fulfill the requirements of SANCO/12495/2011 standard for both sample&nbsp;</span><span style="font-size: 12px;">pretreatment procedures providing results for accuracy (R, 73.1&ndash;118.3%), repeatability (RSD, 3.28&ndash;</span><span style="font-size: 12px;">10.40%) and within-laboratory reproducibility (RSD, 6.45&ndash;17.70%), limits of detection (LOD, 1.5&ndash;2.5&nbsp;</span><span style="font-size: 12px;">g&micro; kg</span>^{<span style="font-size: 12px;">-1</span>}<span style="font-size: 12px;">) and quantification (LOQ, 5.0&ndash;10.0 &micro;g kg</span>^{<span style="font-size: 12px;">-1</span>}<span style="font-size: 12px;">). For the first time, more than 100 honey samples&nbsp;</span><span style="font-size: 12px;">collected from all 7 counties of Autonomous Province of Vojvodina were analyzed. The presence of&nbsp;</span><span style="font-size: 12px;">thiacloprid, imidacloprid and thiametoxam was discovered in a small number of samples. The objective&nbsp;</span><span style="font-size: 12px;">of next study was to develop an optimized LC-MS/MS analytical method with DLLME and QuEChERS&nbsp;</span><span style="font-size: 12px;">procedures for analysis of 7 neonicotinoids in honey liqueur. The method was validated to fulfill the&nbsp;</span><span style="font-size: 12px;">requirements of SANCO/12495/2011 for both sample pretreatment procedures providing results for&nbsp;</span><span style="font-size: 12px;">accuracy (R, 69.2&ndash;113.4% for DLLME; 71.8&ndash;94.9% for QuEChERS), precision (RSD expressed in&nbsp;</span><span style="font-size: 12px;">terms of repeatability (3.21&ndash;10.20% for DLLME; 4.19&ndash;12.81% for QuEChERS) and within-laboratory&nbsp;</span><span style="font-size: 12px;">reproducibility (9.11&ndash;16.63% for DLLME; 11.32&ndash;16.40% for QuEChERS)), limits of detection (LOD,&nbsp;</span><span style="font-size: 12px;">0.5&ndash;1.5 g&micro; L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for DLLME; 1.0&ndash;2.5 g&micro; L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for QuEChERS) and quantification (LOQ, 1.0&ndash;5.0 g&micro; L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for&nbsp;</span><span style="font-size: 12px;">DLLME; 2.5&ndash;10.0 &micro;g L</span>^{<span style="font-size: 12px;">-1&nbsp;</span>}<span style="font-size: 12px;">for QuEChERS). Analysis of real honey liqueur samples obtained from local&nbsp;</span><span style="font-size: 12px;">markets showed the presence of clothianidin or thiacloprid in four of the analyzed samples, therefore&nbsp;</span><span style="font-size: 12px;">implicating the necessity of ongoing control of this type of traditional product. &nbsp;Removal of selected&nbsp;</span><span style="font-size: 12px;">neonicitinoid insecticides - dinotefuran, clothianidin and thiacloprid using MWCNT and H</span><span style="font-size: 12px;">₂O_2&nbsp;</span><span style="font-size: 12px;">from&nbsp;</span><span style="font-size: 12px;">Danube water matrix was investigated. &nbsp;Efficiency of different systems for neonicotinoids removal&nbsp;</span><span style="font-size: 12px;">(under natural insolation in laboratory, with H</span><span style="font-size: 12px;">₂O₂, with MWCNT, with MWCNT+ H</span><span style="font-size: 12px;">₂O₂, with Fe-MWCNT, with Fe-MWCNT+H₂O₂) was evaluated with developed LC-MS/MS method. Analysis of&nbsp;</span><span style="font-size: 12px;">degradation rates revealed loss of 25% of the initial neonicotinoid concentration under natural insolation in&nbsp;</span><span style="font-size: 12px;">the laboratory conditions during 60 min. Addition of chemical agent H₂O_2&nbsp;promoted loss of 40% of the&nbsp;</span><span style="font-size: 12px;">initial dinotefuran, 70% of thiacloprid concentration and total removal of clothianidin under same&nbsp;</span><span style="font-size: 12px;">conditions. With the addition &nbsp;of MWCNT concentration of dinotefuran, clothianidin and thiacloprid&nbsp;</span><span style="font-size: 12px;">decayed for 30, 50 and 60%, respectively. Iron modification of MWCNT in combination with H</span><span style="font-size: 12px;">₂O_2&nbsp;</span><span style="font-size: 12px;">increased the removal rate of selected neonicotinoid for 15&ndash;50%. Presence of intermediates was&nbsp;</span><span style="font-size: 12px;">discovered in systems of dinotefuran with H₂O₂, MWCNT+H</span><span style="font-size: 12px;">₂O₂, e-MWCNT+H₂O_2&nbsp;</span><span style="font-size: 12px;">and of&nbsp;</span><span style="font-size: 12px;">clothianidin in systems with Fe-MWCNT+H₂O_2&nbsp;</span><span style="font-size: 12px;">with m/z of 117,5 and 140,6.&nbsp;</span></p>

New derivatives of carbon nanostructures: nanotubes, nano-onions and nanocrystalline diamonds were obtained through fluorination and subsequent functionalization with sucrose. Chemically modified nanocarbons show high solubility in water, ethanol, DMF and can be used as biomaterials for medical applications. It was demonstrated that sucrose functionalized nanostructures can find applications in nanocomposites due to improved dispersion enabled by polyol functional groups. Additionally, pristine and chemically derivatized carbon nanotubes were studied as nanofillers in epoxy composites. Carbon nanotubes tailored with amino functionalities demonstrated better dispersion and crosslinking with epoxy polymer yielding improved tensile strength and elastic properties of nanocomposites. Reductive functionalization of nanocarbons, also known as Billups reaction, is a powerful method to yield nanomaterials with high degree of surface functionalization. In this method, nanocarbon salts prepared by treatment with lithium or sodium in liquid ammonia react readily with alkyl and aryl halides as well as bromo carboxylic acids. Functionalized materials are soluble in various organic or aqueous solvents. Water soluble nanodiamond derivatives were also synthesized by reductive functionalization of annealed nanodiamonds. Nanodiamond heat pretreatment was necessary to yield surface graphene layers and facilitate electron transfer from reducing agent to the surface of nanoparticles. Other carbon materials such as activated carbon and anthracite coal were also derivatized using reductive functionalization to yield water soluble activated carbon and partially soluble in organic solvents anthracite. It was shown that activated carbon can be effectively functionalized by Billups method. New derivatives of activated carbon can improve water treatment targeting specific impurities and bio active contaminants. It was demonstrated that functionalized carbon nanotubes are suitable for real time radiation measurements. Radiation sensor incorporating derivatized carbon nanotubes is lightweight and reusable. In summary, functionalization of carbon nanomaterials opens new avenues for processing and applications ranging from biomedicine to radiation sensing in space.