Academic literature on the topic 'Organic-inorganic c'

This study assesses the effect of long-term (59 years) application of organic and inorganic fertilizers on soil organic matter and enzyme activity. Total organic C, total organic N, hot water soluble C, microbial biomass C and dehydrogenase activity were evaluated in soil from the long-term field experiment in Prague-Ruzyně (Orthic Luvisol, clay loam). Total organic C and N increased significantly in soils treated with organic fertilizers (farmyard manure, compost) and in soils with a combination of organic and mineral NPK fertilizers (manure + NPK, compost + NPK, cattle manure + straw + NPK) compared to soil treated with inorganic fertilizer, cattle slurry + straw and non-fertilized control. Farmyard manure significantly increased hot water soluble C compared to the control. Dehydrogenase activity was significantly increased by all treatments compared to control. The results indicate that additions of organic matter from various sources differ in the effects on soil organic matter and biological activity. The effect of manure was the most favourable; long-term application of cattle slurry + straw is rather similar to mineral fertilization.

The effect of liming on different organic and inorganic carbon forms in soil was studied in a pot experiment on acidic sandy soil (pH(H2O)=4.38; pH(KCl)=3.42). We used three kinds of liming doses (which were signed M1, M2, M3,). M1 was half of the M2 dose; M2 was the calculated lime dose and M3 was one and the half dose of M2. Lime (CaCO3) was mixed into the soil in powdery form. In addition to liming treatments, a uniform N, P and K treatment (1-1-1g N, P2O5 and K2O per pot) was given. Water supply was set up to 75% field water capacity of soil. Pots were watered daily. During the vegetation period soil and plant (oats; Avena sativa L.) samples were taken from each treatment three times (after 6-10-15 weeks). We determined inorganic- and total-C of the soil by Vario EL element analyser (based on dry combustion method) and calculated the organic-C.The conclusions can be summarized as follows:– Liming treatments had a significant positive effect on the soil-pH and caused quantitative change of different carbon forms of soil.– Increasing tendency of liming doses caused more intensive changes in inorganic- and organic-C forms of soil.– A significant correlations was found between the soil pH and the inorganic-C fraction of soil.– A decreasing correlation was found between the vegetation period and the organic-C fraction.

Porous materials were prepared by sintering using C as place holder and SiO2 as based, mixed with paraffin. Then Organic-inorganic Core-shell Particles were made by crushed. With the help of XRD and SEM, on the 60°C Study on Sulfate-Corrosion Resistance of cement Mixed with Organic-inorganic Core-shell of Preparation. The Organic-inorganic Core-shell Particles made by accounted of C 15% and heat preservation 4h in 920°C were the best. The results showed that when the content of Organic-inorganic Core-shell Particles was 15%, the Sulfate-Corrosion Resistance reached the climax.

With their ability to dissolve inorganic as well as organic materials, ionic liquids have emerged as a versatile solvent system for a diverse range of organic transformations. In the past few decades, the literature has witnessed remarkable advances in a wide range of organic conversions carried out in the presence of various imidazolium, pyridinium, pyrrolidinium, quinolinium and diazobicyclo-octane based ionic liquids. In the reaction, ionic liquids serve as a solvent, catalyst or sometimes both. In certain cases, they are also modified with metal nanoparticles or complexes to form heterogeneous catalysts or are immobilized onto solid support like agar-agar to act as solid-support catalysts. Reactions catalysed by ionic liquids incorporating chiral catalysts possess the advantageous features of being highly enantioselective and reproducible, besides being economical and easy to handle. In this review, an updated insight regarding the role played by ionic liquids in various C-C bond-forming organic reactions, has been summarized.

Selenium chemistry became, over the last 30 years, particularly useful for synthetic organic chemistry [1]. Inorganic as well as organic selenium compounds allow transformation which otherwise cannot be done or require much more drastic conditions to proceed. We have over the last 25 years explored the reactivity of elemental selenium as well as its inorganic and organic derivatives. We report here our recent finding concerning (i) organic diselenols and -diselenolates and (ii) the role of selenoxides in the enantioselective dihydroxylation of C,C double bonds using catalytic amounts of osmium tetroxide.

SUMMARYLong-term fertilization experiment has been conducted since 1981 to study the effect of soil management practices on soil fertility, soil carbon and nitrogen sequestration, soil culturable microbe counts and crop yields at the Nanhu Experimental Station in the Hubei Academy of Agricultural Sciences (situated in the middle reach of the Yangtze River and the rice–wheat cropping system). The experiment was designed with the following eight treatments: (1) unfertilized treatment: Control; (2) inorganic nitrogen fertilizer treatment: N; (3) inorganic nitrogen plus inorganic phosphorus fertilizer treatment: NP; (4) inorganic nitrogen, inorganic phosphorus plus inorganic potassium fertilizer treatment: NPK; (5) pig dung compost (manure) treatment: M; (6) inorganic nitrogen fertilizer plus manure: NM; (7) inorganic nitrogen, inorganic phosphorus fertilizer plus manure treatment: NPM and (8) inorganic nitrogen, inorganic phosphorus, inorganic potassium fertilizer plus manure treatment: NPKM. The results showed that long-term application of organic manure in combination with inorganic fertilizer significantly (p < 0.05) increased soil organic C concentrations compared with the corresponding inorganic fertilizers alone. Soil organic C contents were significantly (p < 0.05) increased in balanced application of NPK fertilizers in comparison to unbalanced application of fertilizers. After 30 years of experiment, soil organic C and total N sequestration rate averagely were 0.48 t ha−1 year−1 and 28.3 kg ha−1 year−1 in the fertilized treatments respectively; nevertheless, it were 0.27 t ha−1 year−1 and 9.7 kg ha−1 year−1 in the unfertilized treatment. Application of organic fertilizer in combination with inorganic fertilizer significantly (p < 0.05) increased culturable microbial counts compared with the corresponding inorganic fertilizers alone. The balanced application of NPK fertilizers significantly (p < 0.05) increased culturable microbial counts compared with unbalanced application of fertilizers. The average grain yield of wheat and rice was significantly (p < 0.05) higher in organic manure combined with inorganic fertilizer treatment than in inorganic fertilizer alone and unfertilized control. Therefore, long-term application of organic manure combined with inorganic fertilizer and balanced application of NPK fertilizers could increase soil organic C and total N sequestration, culturable microbial counts and crop grain yields.

In this work the redox properties of cytochrome c nitrite reductase (CcNiR), a decaheme homodimer that was isolated from S. oneidensis, were determined in the presence and absence of the strong-field ligands cyanide and nitrite. Four hemes per CcNiR protomer are hexa-coordinate with tightly bound axial histidines, while the fifth (active site) has one tightly bound lysine and a distal site that can be open, or contain exogenous ligands such as the substrate nitrite. Controlled potential electrolysis in combination with UV/visible absorption (UV-vis) and electron paramagnetic resonance (EPR) spectroscopies allowed for assignment of all heme midpoint potentials under each set of conditions. The studies show that the active-site heme is the first to be reduced under all conditions. The midpoint redox potential of that heme shifts approximately 70mV to the positive upon binding a strong field ligand such as nitrite or cyanide. When controlled potential electrolysis was carried out in the presence of nitrite, a concerted two electron reduction was observed by UV-vis, and a {Fe(NO)}⁷ reduced product was revealed in EPR. In addition, an asymmetry in ligand binding between active sites was revealed. This information is relevant for the interpretation of planned and ongoing mechanistic studies of CcNiR.

Over-expression, partial purification and characterization of another S. oneidensis multiheme enzyme, known as octaheme tetrathionate reductase (OTR), is also described herein. Though of unknown cellular function, OTR was previously reported to have tetrathionate reductase activity, in addition to nitrite and hydroxylamine reductase activities. The new results indicate that the expression of OTR has no effect on tetrathionate or nitrite reductase activities in the whole cell lysate, and only hydroxylamine reductase activity was substantially elevated in the overexpressing bacteria. OTR was stable in buffered solutions, but substantial activity loss during all attempts at column chromatography was a major obstacle to the complete purification. OTR also proved quite hydrophobic, so possible membrane association should be considered in future attempts to purify this protein.

Finally, this dissertation also reports attempts to improve S. oneidensis' ability to express foreign proteins. Though ideally suited to expressing c-hemes, it proved difficult to express carboxy his-tagged proteins in S. oneidensis because of persistent tag degradation. Attempts to knock out lon protease, a cytoplasmic carboxypeptidase, as well as the result of redirecting ccNiR from the SecA to the possibly more protected signal particle recognition (SRP) secretion pathway, are described.

Iron heme cofactors are single-electron transport moieties that play a crucial role in respiration. While oxygen is the electron acceptor of choice in aerobic atmospheres, microorganisms that live in anaerobic environments utilize other molecules with similarly high reduction potentials. S. oneidensis can utilize numerous terminal electron acceptors, including nitrite, dimethylsulfoxide and even uranium, thanks to a particularly rich array of multi c-heme respiratory proteins. Understanding of how the midpoint potentials and heme arrangements within the proteins influence these exotic respiratory processes is of interest in the fields of bioremediation and fuel development.

The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl2bpy)2(OH2)2](Z)2 (2, Z = CF3SO3; 3, Z = (3,5-(CF3)2C6H3)4B ,i.e. BArF), cis-[Ru(4,4′-Cl2bpy)2(OH2)2](Z)2 (4, Z = CF3SO3; 5, Z = BArF) and cis-[Ru(bpy)2(PR3)(OH2)](CF3SO3)2 (7, bpy = 2,2’-bipyridine, PR3 = P(C6H4F)3; 8, bpy = 2,2-bipyridine, PR3 = PPh3; 9, bpy = 4,4’-dichloro-2,2’-bipyridine, PR3 = PPh3; 10, bpy = 4,4’-dimethyl-2,2’-bipyridine, PR3 = P(C6H4F)3) for the hydrogenation and hydrogenolysis of furfural (FFR), furfuryl alcohol (FFA) and 5-hydroxymethylfurfural (HMF) was investigated. The compounds 2-5 are active and highly selective catalysts for the hydrogenation of FFR to FFA. Using 2 as catalyst at 100 °C, hydrogenation of FFR proceeded to high conversion (≥98%) and with 100% selectivity to FFA in 2 h. The catalyst cis-[Ru(6,6′-Cl2bpy)2(OH2)2](CF3SO3)2 (2) also showed some activity for hydrogenolysis of FFR and FFA at 130 °C in ethanol, giving up to 25% of 2-methylfuran (MF) yield. The catalyst 3 alsodisplayed high catalytic activity for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Catalysts 7-10 are also active towards the hydrogenation of furfural (FFR) in NMP giving >90% FFR conversion with 100% selectivity for furfuryl alcohol (FFA) in 12 h. Compounds 7-10 are active C-O bond hydrogenolysis catalysts in presence of bismuth halide Lewis acids. For example, hydrogenolysis of FFA in the presence of 1 mol% of catalyst cis-[Ru(4,4’-Cl2bpy)2(PPh3)(OH2)](CF3SO3)2 (9) and 20 mol% bismuth bromide at 180 °C/51 atm H2 pressure gave >96% conversion of FFA and 55% MF yield. Compounds 7-10 in the presence of bismuth halides, showed almost 100% conversion of HMF with a very high selectivity (65-72%) for 2,5-DMF, along with 10-12% of MF, and trace amount of 5-methylfurfural (MeFFR). In order to test the activity of ruthenium hydrides towards the C-O bond hydrogenation and hydrogenolysis of HMF, series of monocationic ruthenium complexes cis-[Ru(bpy)2(PR3)(H)](CF3SO3) (12, bpy = 2,2’-bipyridine, PR3 = P(C6H4F)3; 13, bpy = 2,2-bipyridine, PR3= PPh3; 14, bpy = 4,4’-dimethyl-2,2’-bipyridine, PR3= P(C6H4F)3) were prepared. The hydrogenation of HMF using catalysts 12-14, produced 70-72% of 2,5-DMF and 11% MF, suggesting that ruthenium hydrides are active and efficient catalysts for HMF hydrogenation.

Development of synthetic routes toward two general organometallic frameworks was undertaken. The first project involved synthetic attempts of substituted and unsubstituted ferroceno[c]thiophene while the second one was the synthesis of 1,2-dithienylmetallocenes. The long-term goal of this work is to lay the foundations for study of electronic, electrochromic, redox, and optical properties of thiophene-based materials integrated with organometallic systems such as ferrocene, ruthenocene and cymantrene. The synthetic pathway for the target molecule in the first project involved converting 1,2-bis(hydroxymethyl)ferrocene to 1,2-bis(thiouroniummethyl)ferrocene with thiourea under acidic conditions. Refluxing the salt in base followed by acidification resulted in 1,2-bis(mercaptomethyl)ferrocene, which is oxidized to the cyclic ferroceno[d]-1,2-dithiane. Ring contraction of cyclic dithiane gave the thioether, ferroceno[c]-2,5-dihydrothiophene. Periodate oxidation of the thioether gave ferroceno[c]-2,5-dihydrothiophene-S-oxide (1), a potential precursor for ferroceno[c]thiophene via Pummerer dehydration. Attempts to dehydrate 1 and to trap the resulting thiophene in situ indicated instability of the target compound. Synthesis of ferroceno[c]thiophene with electron-donating as well as electron-withdrawing substituents at the 2,5-positions of the thiophene ring was attempted. 1,2–Dithienylethenes and their derivatives have gained increased attention due to their exceptional photochromic property. They tend to be thermally irreversible but photochemically reversible, which is a vital for their potential use in optical memories, switches and other optoelectronic applications. Inspiration of the second project was that incorporation of 1,2-dithienyl systems into metallocenes would enhance the general properties of the molecule, including stability, fatigue resistance, solid-state reactivity and higher sensitivity. 1,2-Dithienylferrocene was successfully synthesized. The synthetic pathway for 1,2-dithienylferrocene involved the reaction of α-bromo-3-acetyl-2,5-dimethylthiophene (1) with ethyl 4-(2,5-dimethylthiophen-3-yl)-3-oxobutanoate (2) to give 2,3-diarylcyclopent-2-en-1-one (3). Compounds 1 and 2 were synthesized following literature methods. Compound 3 was then converted to its cyclopentadienide form by first reducing the ketone to alcohol using LAH, followed by dehydration and then deprotonation of the substituted cyclic diene using butyllithium to give 1,2-bis(2,5-dimethylthiophene)-2,4-cyclopentadien-1-yl)lithium (4). [Fe(fluorenyl)(Cp)] was then used as a transfer reagent and reacted with 4 to yield the target compound.

Four molecular germanates based on salicyl alcoholates, bis(dimethylammonium) tris[2-(oxidomethyl)phenolate(2-)]germanate (1), bis(dimethylammonium) tris[4-methyl-2-(oxidomethyl)phenolate(2-)]germanate (2), bis(dimethylammonium) tris[4-bromo-2-(oxidomethyl)phenolate(2-)]germanate (3) and dimethylammonium bis[2-tert-butyl-4-methyl-6-(oxidomethyl)phenolate(2-)][2-tert-butyl-4-methyl-6-(hydroxymethyl)phenolate(1-)]germanate (4), were synthesized and characterized including single crystal X-ray diffraction analysis. In the solid state, compounds 1 and 2 exhibit one-dimensional hydrogen bonded networks, whereas compound 4 forms separate ion pairs, which are connected by hydrogen bonds between the dimethylammonium and the germanate moieties. The potential of these compounds for thermally induced twin polymerization (TP) was studied. Germanate 1 was converted by TP to give a hybrid material (HM-1) composed of phenolic resin and germanium dioxide. Subsequent reduction with hydrogen provided a microporous composite containing crystalline germanium and carbon (Ge@C – C-1, germanium content ∼20%). Studies on C-1 as an anode material for Li-ion batteries revealed reversible capacities of ∼370 mA h gGe@C−1 at a current density up to 1384 mA g−1 without apparent fading for 500 cycles
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Bones are multifunctional passive organs of movement that supports soft tissue and directly attached muscles. They also protect internal organs and are a reserve of calcium, phosphorus and magnesium. Each bone is covered with periosteum, and the adjacent bone surfaces are covered by articular cartilage. Histologically, the bone is an organ composed of many different tissues. The main component is bone tissue (cortical and spongy) composed of a set of bone cells and intercellular substance (mineral and organic), it also contains fat, hematopoietic (bone marrow) and cartilaginous tissue. Bones are a tissue that even in adult life retains the ability to change shape and structure depending on changes in their mechanical and hormonal environment, as well as self-renewal and repair capabilities. This process is called bone turnover. The basic processes of bone turnover are: • bone modeling (incessantly changes in bone shape during individual growth) following resorption and tissue formation at various locations (e.g. bone marrow formation) to increase mass and skeletal morphology. This process occurs in the bones of growing individuals and stops after reaching puberty • bone remodeling (processes involve in maintaining bone tissue by resorbing and replacing old bone tissue with new tissue in the same place, e.g. repairing micro fractures). It is a process involving the removal and internal remodeling of existing bone and is responsible for maintaining tissue mass and architecture of mature bones. Bone turnover is regulated by two types of transformation: • osteoclastogenesis, i.e. formation of cells responsible for bone resorption • osteoblastogenesis, i.e. formation of cells responsible for bone formation (bone matrix synthesis and mineralization) Bone maturity can be defined as the completion of basic structural development and mineralization leading to maximum mass and optimal mechanical strength. The highest rate of increase in pig bone mass is observed in the first twelve weeks after birth. This period of growth is considered crucial for optimizing the growth of the skeleton of pigs, because the degree of bone mineralization in later life stages (adulthood) depends largely on the amount of bone minerals accumulated in the early stages of their growth. The development of the technique allows to determine the condition of the skeletal system (or individual bones) in living animals by methods used in human medicine, or after their slaughter. For in vivo determination of bone properties, Abstract 10 double energy X-ray absorptiometry or computed tomography scanning techniques are used. Both methods allow the quantification of mineral content and bone mineral density. The most important property from a practical point of view is the bone’s bending strength, which is directly determined by the maximum bending force. The most important factors affecting bone strength are: • age (growth period), • gender and the associated hormonal balance, • genotype and modification of genes responsible for bone growth • chemical composition of the body (protein and fat content, and the proportion between these components), • physical activity and related bone load, • nutritional factors: – protein intake influencing synthesis of organic matrix of bone, – content of minerals in the feed (CA, P, Zn, Ca/P, Mg, Mn, Na, Cl, K, Cu ratio) influencing synthesis of the inorganic matrix of bone, – mineral/protein ratio in the diet (Ca/protein, P/protein, Zn/protein) – feed energy concentration, – energy source (content of saturated fatty acids - SFA, content of polyun saturated fatty acids - PUFA, in particular ALA, EPA, DPA, DHA), – feed additives, in particular: enzymes (e.g. phytase releasing of minerals bounded in phytin complexes), probiotics and prebiotics (e.g. inulin improving the function of the digestive tract by increasing absorption of nutrients), – vitamin content that regulate metabolism and biochemical changes occurring in bone tissue (e.g. vitamin D3, B6, C and K). This study was based on the results of research experiments from available literature, and studies on growing pigs carried out at the Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences. The tests were performed in total on 300 pigs of Duroc, Pietrain, Puławska breeds, line 990 and hybrids (Great White × Duroc, Great White × Landrace), PIC pigs, slaughtered at different body weight during the growth period from 15 to 130 kg. Bones for biomechanical tests were collected after slaughter from each pig. Their length, mass and volume were determined. Based on these measurements, the specific weight (density, g/cm3) was calculated. Then each bone was cut in the middle of the shaft and the outer and inner diameters were measured both horizontally and vertically. Based on these measurements, the following indicators were calculated: • cortical thickness, • cortical surface, • cortical index. Abstract 11 Bone strength was tested by a three-point bending test. The obtained data enabled the determination of: • bending force (the magnitude of the maximum force at which disintegration and disruption of bone structure occurs), • strength (the amount of maximum force needed to break/crack of bone), • stiffness (quotient of the force acting on the bone and the amount of displacement occurring under the influence of this force). Investigation of changes in physical and biomechanical features of bones during growth was performed on pigs of the synthetic 990 line growing from 15 to 130 kg body weight. The animals were slaughtered successively at a body weight of 15, 30, 40, 50, 70, 90, 110 and 130 kg. After slaughter, the following bones were separated from the right half-carcass: humerus, 3rd and 4th metatarsal bone, femur, tibia and fibula as well as 3rd and 4th metatarsal bone. The features of bones were determined using methods described in the methodology. Describing bone growth with the Gompertz equation, it was found that the earliest slowdown of bone growth curve was observed for metacarpal and metatarsal bones. This means that these bones matured the most quickly. The established data also indicate that the rib is the slowest maturing bone. The femur, humerus, tibia and fibula were between the values of these features for the metatarsal, metacarpal and rib bones. The rate of increase in bone mass and length differed significantly between the examined bones, but in all cases it was lower (coefficient b <1) than the growth rate of the whole body of the animal. The fastest growth rate was estimated for the rib mass (coefficient b = 0.93). Among the long bones, the humerus (coefficient b = 0.81) was characterized by the fastest rate of weight gain, however femur the smallest (coefficient b = 0.71). The lowest rate of bone mass increase was observed in the foot bones, with the metacarpal bones having a slightly higher value of coefficient b than the metatarsal bones (0.67 vs 0.62). The third bone had a lower growth rate than the fourth bone, regardless of whether they were metatarsal or metacarpal. The value of the bending force increased as the animals grew. Regardless of the growth point tested, the highest values were observed for the humerus, tibia and femur, smaller for the metatarsal and metacarpal bone, and the lowest for the fibula and rib. The rate of change in the value of this indicator increased at a similar rate as the body weight changes of the animals in the case of the fibula and the fourth metacarpal bone (b value = 0.98), and more slowly in the case of the metatarsal bone, the third metacarpal bone, and the tibia bone (values of the b ratio 0.81–0.85), and the slowest femur, humerus and rib (value of b = 0.60–0.66). Bone stiffness increased as animals grew. Regardless of the growth point tested, the highest values were observed for the humerus, tibia and femur, smaller for the metatarsal and metacarpal bone, and the lowest for the fibula and rib. Abstract 12 The rate of change in the value of this indicator changed at a faster rate than the increase in weight of pigs in the case of metacarpal and metatarsal bones (coefficient b = 1.01–1.22), slightly slower in the case of fibula (coefficient b = 0.92), definitely slower in the case of the tibia (b = 0.73), ribs (b = 0.66), femur (b = 0.59) and humerus (b = 0.50). Bone strength increased as animals grew. Regardless of the growth point tested, bone strength was as follows femur > tibia > humerus > 4 metacarpal> 3 metacarpal> 3 metatarsal > 4 metatarsal > rib> fibula. The rate of increase in strength of all examined bones was greater than the rate of weight gain of pigs (value of the coefficient b = 2.04–3.26). As the animals grew, the bone density increased. However, the growth rate of this indicator for the majority of bones was slower than the rate of weight gain (the value of the coefficient b ranged from 0.37 – humerus to 0.84 – fibula). The exception was the rib, whose density increased at a similar pace increasing the body weight of animals (value of the coefficient b = 0.97). The study on the influence of the breed and the feeding intensity on bone characteristics (physical and biomechanical) was performed on pigs of the breeds Duroc, Pietrain, and synthetic 990 during a growth period of 15 to 70 kg body weight. Animals were fed ad libitum or dosed system. After slaughter at a body weight of 70 kg, three bones were taken from the right half-carcass: femur, three metatarsal, and three metacarpal and subjected to the determinations described in the methodology. The weight of bones of animals fed aa libitum was significantly lower than in pigs fed restrictively All bones of Duroc breed were significantly heavier and longer than Pietrain and 990 pig bones. The average values of bending force for the examined bones took the following order: III metatarsal bone (63.5 kg) <III metacarpal bone (77.9 kg) <femur (271.5 kg). The feeding system and breed of pigs had no significant effect on the value of this indicator. The average values of the bones strength took the following order: III metatarsal bone (92.6 kg) <III metacarpal (107.2 kg) <femur (353.1 kg). Feeding intensity and breed of animals had no significant effect on the value of this feature of the bones tested. The average bone density took the following order: femur (1.23 g/cm3) <III metatarsal bone (1.26 g/cm3) <III metacarpal bone (1.34 g / cm3). The density of bones of animals fed aa libitum was higher (P<0.01) than in animals fed with a dosing system. The density of examined bones within the breeds took the following order: Pietrain race> line 990> Duroc race. The differences between the “extreme” breeds were: 7.2% (III metatarsal bone), 8.3% (III metacarpal bone), 8.4% (femur). Abstract 13 The average bone stiffness took the following order: III metatarsal bone (35.1 kg/mm) <III metacarpus (41.5 kg/mm) <femur (60.5 kg/mm). This indicator did not differ between the groups of pigs fed at different intensity, except for the metacarpal bone, which was more stiffer in pigs fed aa libitum (P<0.05). The femur of animals fed ad libitum showed a tendency (P<0.09) to be more stiffer and a force of 4.5 kg required for its displacement by 1 mm. Breed differences in stiffness were found for the femur (P <0.05) and III metacarpal bone (P <0.05). For femur, the highest value of this indicator was found in Pietrain pigs (64.5 kg/mm), lower in pigs of 990 line (61.6 kg/mm) and the lowest in Duroc pigs (55.3 kg/mm). In turn, the 3rd metacarpal bone of Duroc and Pietrain pigs had similar stiffness (39.0 and 40.0 kg/mm respectively) and was smaller than that of line 990 pigs (45.4 kg/mm). The thickness of the cortical bone layer took the following order: III metatarsal bone (2.25 mm) <III metacarpal bone (2.41 mm) <femur (5.12 mm). The feeding system did not affect this indicator. Breed differences (P <0.05) for this trait were found only for the femur bone: Duroc (5.42 mm)> line 990 (5.13 mm)> Pietrain (4.81 mm). The cross sectional area of the examined bones was arranged in the following order: III metatarsal bone (84 mm2) <III metacarpal bone (90 mm2) <femur (286 mm2). The feeding system had no effect on the value of this bone trait, with the exception of the femur, which in animals fed the dosing system was 4.7% higher (P<0.05) than in pigs fed ad libitum. Breed differences (P<0.01) in the coross sectional area were found only in femur and III metatarsal bone. The value of this indicator was the highest in Duroc pigs, lower in 990 animals and the lowest in Pietrain pigs. The cortical index of individual bones was in the following order: III metatarsal bone (31.86) <III metacarpal bone (33.86) <femur (44.75). However, its value did not significantly depend on the intensity of feeding or the breed of pigs.

Carbon is the key element of life on Earth and exists in more than a million compounds (Holmén, 2000; Berner, 2004). The unique covalent long-chained and aromatic carbon compounds form the basis of organic chemistry and the “roadmap” for understanding life from the cellular to the ecosystem level. The oxidation states of C atoms range from +IV to −IV; methane (CH4) is the most reduced form of C (−IV), with CO2 and other carbonate forms existing in the most oxidized state (+IV). The major reservoirs of C are stored in the Earth’s crust, with much of it as inorganic carbonate and the remaining as organic C (e.g., kerogen) (figure 13.1; Sundquist, 1993). The global C cycle can be divided into short- and long-term cycles based on the vast differences in the turnover times of different C pools (Berner, 2004). The carbonate reservoir can be divided into two primary subreservoirs: (1) dissolved inorganic carbon (DIC) in the ocean (H2CO3, HCO3−, and CO32−), and (2) solid carbonate minerals [CaCO3, CaMg(CO3)2, and FeCO3] (Holmén, 2000). While the global C cycle is quite complex, it is perhaps the best understood of all the bioactive element cycles. In fact, there have been numerous review papers on this cycle (e.g., Keeling, 1973; Degens et al., 1984; Siegenthaler and Sarmiento, 1993; Sundquist, 1993; Schimel et al., 1995; Holmén, 2000). Much of the interest in the global C cycle in recent years stems from linkages with environmental issues concerning carbon-based greenhouse gases (e.g., CO2 and CH4) and their role in global climate change (Dickinson and Cicerone, 1986). As described in chapter 8, short-term controls on the C cycle are largely a function of the uptake of inorganic C by autotrophs to fuel fixation in photosynthesis, and the utilization of organic carbon as a food resource by heterotrophs recycling inorganic C back into the system. This short-term cycle, which allows for the transfer of C between the lithosphere, hydrosphere, biosphere, and atmosphere over periods of days to thousands of years, is relatively short in comparison to the more than 4 billion year age of the Earth.

This chapter sheds light on AC and DC power capacitors and the recent impacts of nanoparticles on enhancing capacitive charge in power capacitors. In addition, this chapter displays theories and effective parameters of nano-tech power capacitors. Lab-test measurements have been carried out for variant sorts and concentrations of organic and inorganic nanoparticles during different frequencies (10mHz – 10MHz) and temperatures (20°C-80°C). Moreover, this chapter reviews the ideal sorts and concentrations of nanoparticles for upgrading the capacitive charging on insulation of power capacitors. Thus, the novel nanodielectrics have been designed and fabricated for upgrading the electrical execution of multi-section metalized film capacitors.

A major focus of the previous six chapters has been on the chemistry and interactions of the HOx, NOx, and volatile organic compound (VOC) families. Details of the reactions of O3 NO3, and HO that act to initiate VOC oxidation have been presented, as has the ensuing chemistry involving organic peroxy and alkoxy radicals and their interactions with NOx. In this chapter, we complete our discussion of thermal chemical reactions that impact tropospheric ozone. The chapter begins with a discussion of the budgets of two simple (inorganic) carbon-containing species not yet discussed, carbon dioxide (CO2) and carbon monoxide (CO). Although CO2 is not directly involved in ozone-related tropospheric chemistry, it is of course the species most critical to discussions of global climate change, and thus a very brief overview of its concentrations, sources, and sinks is presented. CO is a ubiquitous global pollutant, and its reaction with HO is an essential part of the tropospheric background chemistry. This is followed by a presentation of the tropospheric chemistry of halogen species, beginning with a discussion of inorganic halogen cycles that impact (in particular) the ozone chemistry of the marine boundary layer (MBL) and concluding with a detailed presentation of the reactions of Cl atoms and Br atoms with VOC species. The chapter concludes with an overview of tropospheric sulfur chemistry. The reactions leading to the oxidation of inorganic (SO2 and SO3) as well as organic sulfur compounds (e.g., DMS, CH3SCH3) are detailed, and a brief discussion of the effects of the oxidation of sulfur species on aerosol production in the troposphere and stratosphere is also given. The abundance of CO2 in the atmosphere has obviously received a great deal of attention in recent decades due to the influence of this gas on Earth’s climate system. Indeed, changes in the atmospheric CO2 concentration represent the single largest contributor to changes in radiative forcing since preindustrial times (c. 1750). The atmospheric burden of CO2 is controlled by the processes that make up the global carbon cycle—the exchanges of carbon (mostly in the form of CO2) between various “reservoirs,” including the atmosphere, land (vegetation and soil), the surface ocean, the intermediate and deep ocean, sediment on the ocean floor, and the fossil fuel reservoir (IPCC, 2007).

<em>Abstract.—</em>Organic material can enter aquatic systems by de novo gross primary production (GPP) from inorganic carbon within the system (autochthonous sources) or by import from the surrounding watershed and upstream aquatic systems (allochthonous sources). We analyzed the spatio–temporal variation in these two organic carbon sources for the 150-km long tidal freshwater Hudson during 2 years (1999 and 2000). Gross primary production was calculated from dawn– dusk sampling at 2-km intervals over the length of the Estuary for dissolved oxygen, pH, and DIC. Allochthonous inputs (All) were also calculated for the same periods based on organic carbon measurements and hydrologic flows. The relative importance of these two organic carbon sources (GPP/All) varied by over 30-fold across space and time. This variation was related to hydrologic inputs; on average 1999 (the second driest summer in the past 15 years) had 10- fold greater GPP/All than did 2000 (the wettest summer in 15 years). Associated with the high GPP/All in 2000 there was higher carbon dioxide supersaturation and net heterotrophy as compared to 1999. We suggest that hydrologically driven variation in GPP/All may also impact the food web and the dominant organic carbon source for fish and invertebrate consumers in the river. Natural abundance ¹⁴C measurements could potentially trace these two food sources as they vary in space and time.

<em>Abstract.—</em>Organic material can enter aquatic systems by de novo gross primary production (GPP) from inorganic carbon within the system (autochthonous sources) or by import from the surrounding watershed and upstream aquatic systems (allochthonous sources). We analyzed the spatio–temporal variation in these two organic carbon sources for the 150-km long tidal freshwater Hudson during 2 years (1999 and 2000). Gross primary production was calculated from dawn– dusk sampling at 2-km intervals over the length of the Estuary for dissolved oxygen, pH, and DIC. Allochthonous inputs (All) were also calculated for the same periods based on organic carbon measurements and hydrologic flows. The relative importance of these two organic carbon sources (GPP/All) varied by over 30-fold across space and time. This variation was related to hydrologic inputs; on average 1999 (the second driest summer in the past 15 years) had 10- fold greater GPP/All than did 2000 (the wettest summer in 15 years). Associated with the high GPP/All in 2000 there was higher carbon dioxide supersaturation and net heterotrophy as compared to 1999. We suggest that hydrologically driven variation in GPP/All may also impact the food web and the dominant organic carbon source for fish and invertebrate consumers in the river. Natural abundance ¹⁴C measurements could potentially trace these two food sources as they vary in space and time.

Natural organic matter (NOM) is a major intermediate in the global carbon, nitrogen, sulfur, and phosphorus cycles. NOM is also the environmental matrix that frequently controls binding, transport, degradation, and toxicity of many organic and inorganic contaminants. Despite its importance, NOM is poorly understood at the structural chemistry level because of its molecular complexity and heterogeniety. Nuclear magnetic resonance (NMR) spectroscopy is one of the most useful spectrometric methods used to investigate NOM structure because qualitative and quantitative organic structure information for certain organic elements can be generated by NMR for NOM in both the solution and solid states under nondegradative conditions. However, NMR spectroscopy is not as sensitive as infrared or ultraviolet-visible spectroscopy; it is not at present applicable to organic oxygen and sulfur, and quantification of NMR spectra is difficult under certain conditions. The purpose of this overview is to present briefly the “state of the art” of NMR characterization of NOM, and to suggest future directions for NMR research into NOM. More comprehensive texts concerning the practice of NMR spectroscopy and its application to NOM in various environments have been produced by Wilson and by Wershaw and Mikita. Carbon, hydrogen, and oxygen are the major elements of NOM; together they comprise about 90% of the mass. The minor elements that constitute the remainder are nitrogen, sulfur, phosphorus, and trace amounts of the various halogen elements. With the exception of coal, in which carbon is the most abundant element, the order of relative abundance in NOM on an atomic basis is H > C > O > N > S > P = halogens. The optimum NMR-active nuclei for these elements are 1H, 13C, 17O, 15N, 33S, 31P, and 19F. The natural abundances and receptivities of these nuclei relative to 1H are given in Table 12.1. Quadrupolar effects for 17O, 33S, and halogen elements other than 19F lead to line broadening that greatly limits resolution in NMR studies of these elements in NOM.

<em>Abstract.</em>—Hudson riverine and coastal marshes provide a paleoecological archive consisting of information on climate and land use at both the local and watershed scales. The timing of formation of these marshes is documented using accelerator mass spectrometry (AMS) ¹⁴C dating of identified plant macrofossils in basal marsh organic sediments. While the Staten Island marsh is oldest and dates to 11,000 years before present (BP), Piermont, Iona, and Croton marshes date to the mid-Holocene, and the Jamaica Bay marshes formed most recently. Pollen and spores, charcoal, and plant macrofossils in the marsh sediments document marked climatic shifts as well as anthropogenic impact in the region. Assessment of the inorganic and organic content of the sediments in the marshes reveals a pattern of decreasing inorganic supply with the arrival of the Europeans, possibly due to the construction of numerous Hudson River tributary dams. Piermont Marsh, because of its sensitive location in the Hudson River, records droughts and wet intervals through species which have specific salinity affinities. Throughout the marsh records, the ragweed <em>Ambrosia </em>pollen rise marks the anthropogenic impact at the landscape scale. The recorded changes in hydrology and salinity that occurred throughout the centuries and millennia would have had profound effects throughout the food web and estuarine ecosystem. Fish populations would have been affected by changes in the food supply due to shifts in runoff affecting turbidity and light penetration in the river. Local vegetation changes within marshes may also have affected juvenile fish populations.

<em>Abstract.</em>—Hudson riverine and coastal marshes provide a paleoecological archive consisting of information on climate and land use at both the local and watershed scales. The timing of formation of these marshes is documented using accelerator mass spectrometry (AMS) ¹⁴C dating of identified plant macrofossils in basal marsh organic sediments. While the Staten Island marsh is oldest and dates to 11,000 years before present (BP), Piermont, Iona, and Croton marshes date to the mid-Holocene, and the Jamaica Bay marshes formed most recently. Pollen and spores, charcoal, and plant macrofossils in the marsh sediments document marked climatic shifts as well as anthropogenic impact in the region. Assessment of the inorganic and organic content of the sediments in the marshes reveals a pattern of decreasing inorganic supply with the arrival of the Europeans, possibly due to the construction of numerous Hudson River tributary dams. Piermont Marsh, because of its sensitive location in the Hudson River, records droughts and wet intervals through species which have specific salinity affinities. Throughout the marsh records, the ragweed <em>Ambrosia </em>pollen rise marks the anthropogenic impact at the landscape scale. The recorded changes in hydrology and salinity that occurred throughout the centuries and millennia would have had profound effects throughout the food web and estuarine ecosystem. Fish populations would have been affected by changes in the food supply due to shifts in runoff affecting turbidity and light penetration in the river. Local vegetation changes within marshes may also have affected juvenile fish populations.

It has been found that metallic TRU waste releases considerable portions of C-14 in the form of organic molecules such as lower molecular weight organic acids, alcohols and aldehydes. Due to the low sorption ability of organic C-14, it is important to clarify the long-term behavior of organic forms under waste disposal conditions. From investigations on radiolytic decomposition of organic carbon molecules into inorganic carbonic acid, it is expected that radiation from TRU waste will decompose organic C-14 into inorganic carbonic acid that has higher adsorption ability into the engineering barriers. Hence we have studied the decomposition behavior of organic C-14 by gamma irradiation experiments under simulated disposal conditions. The results showed that organic C-14 reacted with OH radicals formed by radiolysis of water, to produce inorganic carbonic acid. We introduced the concept of “decomposition efficiency” which expresses the percentage of OH radicals consumed for the decomposition reaction of organic molecules in order to analyze the experimental results. We estimated the effect of radiolytic decomposition on the concentration of organic C-14 in the simulated conditions of the TRU disposal system using the decomposition efficiency, and found that the concentration of organic C-14 in the waste package will be lowered when the decomposition of organic C-14 by radiolysis was taken into account, in comparison with the concentration of organic C-14 without radiolysis. Our prediction suggested that some amount of organic C-14 can be expected to be transformed into the inorganic form in the waste package in an actual system.

Highly selective removal of Cesium and Strontium is critical for waste treatment and environmental remediation. Cesium-137 is a beta-gamma emitter and Strontium-90 is a beta emitter with respective half-lives of 30 and 29 years. Both elements are present at many nuclear sites. Cesium and Strontium can be found in wastewaters at Washington State’s Hanford Site, as well as in wastestreams of many Magnox reactor sites. Cesium and Strontium are found in the Reactor Coolant System of light water reactors at nuclear power plants. Both elements are also found in spent nuclear fuel and in high-level waste (HLW) at DOE sites. Cesium and Strontium are further major contributors to the activity and the heat load. Therefore, technologies to extract Cesium and Strontium are critical for environmental remediation waste treatment and dose minimization. Radionuclides such as Cesium-137 and Strontium-90 are key drivers of liquid waste classification at light water reactors and within the DOE tank farm complexes. The treatment, storage, and disposal of these wastes represents a major cost for nuclear power plant operators, and comprises one of the most challenging technology-driven projects for the DOE Environmental Management (EM) program. Extraction technologies to remove Cesium and Strontium have been an active field of research. Four notable extraction technologies have been developed so far for HLW: solvent extraction, prussian blue, crystalline silicotitanate (CST) and organic ion-exchangers (e.g., resorcinol formaldehyde and SuperLig). The use of one technology over another depends on the specific application. For example, the waste treatment plant (WTP) at Hanford is planning on using a highly-selective organic ion-exchange resin to remove Cesium and Strontium. Such organic ion-exchangers use molecular recognition to selectively bind to Cesium and Strontium. However, these organic ion-exchangers are synthesized using multi-step organic synthesis. The associated cost to synthesize organic ion-exchangers is prohibitive and seriously limits the scope of applications for organic ion-exchangers. Further issues include resin swelling, potential hydrogen generation and precluding final disposal by vitrification without further issues. An alternative to these issues of organic ion-exchangers is emerging. Inorganic ion-exchangers offer a superior chemical, thermal and radiation stability which is simply not achievable with organic compounds. They can be used to remove both Cesium as well as Strontium with a high level of selectivity under a broad pH range. Inorganic ion-exchangers can operate at acidic pH where protons inhibit ion exchange in alternative technologies such as CST. They can also be used at high pH which is typically found in conditions present in many nuclear waste types. For example, inorganic ion-exchangers have shown significant Strontium uptake from pH 1.9 to 14. In contrast to organic ion-exchangers, inorganic ion-exchangers are not synthesized via complex multi-step organic synthesis. Therefore, inorganic ion-exchangers are substantially more cost-effective when compared to organic ion-exchangers as well as CST. Selective removal of specified isotopes through ion exchange is a common and proven treatment method for liquid waste, yet various aspects of existing technologies leave room for improvement with respect to both cost and effectiveness. We demonstrate a novel class of inorganic ion-exchangers for the selective removal of cesium and strontium (with future work planned for uranium removal), the first of a growing family of patent-pending, potentially elutable, and paramagnetic ion-exchange materials [1]. These highly selective inorganic ion-exchangers display strong chemical, thermal and radiation stability, and can be readily synthesized from low-cost materials, making them a promising alternative to organic ion-exchange resins and crystalline silicotitanate (CST). By nature, these inorganic media lend themselves more readily to volume reduction (VR) by vitrification without the issues faced with organic resins. In fact, with a simple melting of the KMS-1 media at 650–670 deg. C (i.e., well below the volatilization temperature of Cs, Sr, Mn, Fe, Sb, etc.), a VR of 4:1 was achieved. With true pyrolysis at higher temperatures or by vitrification, this VR would be much higher. The introduction of this new family of highly specific ion-exchange agents has potential to both reduce the cost of waste processing, and enable improved waste-classification management in both nuclear power plants (for the separation of Class A from B/C wastes) and DOE tank farms [for the separation of low level waste (LLW) from high level waste (HLW)]. In conclusion, we demonstrate for the first time a novel inorganic ion-exchanger for the selective removal of Cesium and Strontium. These inorganic ion-exchangers are chemical, thermal and radiation stable. These inorganic ion-exchangers can be synthesized in a cost-effective way which makes them significantly more effective than organic ion-exchange resin and CST. Finally, new thermal options are afforded for their final volume reduction, storage and disposal.

We introduce the successful fabrication of inorganic polymer derived microchannels with organic solvent resistance and optical transparency, via economic micro-molding process by using two types of source materials: commercial polyvinylsilazane (HTT1800 Kion Corp.), or allylhydropolycarbosilane (SMP-10, Starfire Co.). And we demonstrated the reliable microchemical performance in various organic solvents such as THF, DMF and acetonitrile at elevated temperatures. Knovenagel and Diels-Alder reactions were successfully run by pressured-driven flow in 2 cm and 16 cm long channel, respectively. It is proven that the developed inorganic polymer-based microchannels were obviously performed as a niche material-based microfluidic device between plastic and glass based device. In addition, we present the fabrication and characterization of ceramic microreactors composed of inverted beaded silicon carbide (SiC) monoliths with interconnected pores as catalyst supports, integrated within high-density alumina housings obtained via an optimized gel-casting procedure. These tailored macroporous SiC monoliths deposited Ru as a catalyst was run for the decomposition of ammonia with at temperatures between 450 and 1000 °C, which demonstrated a high temperature fuel cell reformer.

Layered silicate nanolayers can be used as alternative inorganic components for the construction of nanostructured hybrid composites. The clay silicate nanolayers possess stable Si-O bonds and high particle aspect ratios comparable to conventional fibers. Their interlayer surface is easily modified by ion-exchange reaction, and the gallery can be intercalated by organic polymer precursors for the formation of organic-inorganic nanocomposites. Exfoliated clay composites contain single, 1 nm thick layers of clay dispersed in the polymer matrix. Owing to the platy morphology of the silicate layers, exfoliated clay nanocomposites can exhibit dramatically improved properties such as barrier and mechanical properties that are not available for conventional composite materials. Since the clay particles scavenge water, the nanocomposite samples initially absorb slightly higher amounts of water in comparison to the no-clay samples, with the water molecules congregating around the clay particles. On the other hand, the presence of these clay particles still hinders diffusion of water through the sample, thus protecting the structural interfaces. In this work, low viscosity liquid aromatic diglycidyl ether of bisphenol A (DGEBA) epoxy resin Epon 815C was mixed with nanoclay at 60°C for 6 hours. The epoxy-clay mixture was then mixed with curing agent DETA (Diethylenetriamine) at 80°C for 4 minutes and cured at 120°C for 3 hours to produce exfoliated clay — epoxy resin system. These samples were used to first optimize the percent clay level for lowest water uptake, and subsequently immersed in water in stressed condition (flexural stress) to assess the effect of stress on nanocomposite epoxy system for its water uptake behavior. The results revealed up to 33% reduction in water uptake for the stressed samples.

Abstract Melting gels are a class of hybrid organic-inorganic, silica-based sol-gels which are solid below their glass transition temperatures, near room temperature, but show thermoplastic behavior when heated. While this phase change can be repeated multiple times, heating the gel past its consolidation temperature, typically above 130 °C, initiates an irreversible reaction that produces highly crosslinked glassy organic/inorganic materials via hydrolysis and polycondensation. This ability makes melting gels uniquely compatible with processing techniques inaccessible to other sol-gels. By properly tuning their properties, it should be possible to create protective coatings for electronics and anti-corrosive coatings for metals that are highly hydrophobic and insulating. However, melting gel consolidation reactions are highly dependent on charge interactions, raising the question of how these materials will respond to a processing technique, like electrospray deposition (ESD), which is dependent on charge delivery. In this study, we focus on the role that substrate temperature and charge polarity play on film morphology, consolidation chemistry, and surface properties when processing via ESD. Optical images, film thickness measurements, and FTIR were used to characterize the sprayed melting gel with the goal of developing a robust processing space for producing highly cross linked, hydrophobic, dielectric coatings.

The effects of combustion and feeding conditions on Polycyclic Aromatic Hydrocarbons (PAH) and PCDD/F formation and appearance in the emissions at the stack during sludge incineration are discussed in this paper. Partitioning in the solid streams of Cd, Cr, Cu, Mn, Ni, Pb and Zn is also analyzed. Tests were performed on a demonstrative plant equipped with a fluidized bed furnace (FBF) using sewage sludge either as is or spiked with chlorinated organic compounds (tetrachloroethylene or a mixture of tetrachloroethylene, chlorobenzene and toluene) to study the chlorine effect on the presence of micropollutants in the different streams. Exhaust gases were sampled both before and after the treatment system (bag house and wet scrubber). In the untreated flue gas the highest values of PCDD/F and PAH were detected when the afterburning chamber was not in use or operating at low temperatures. Operation of the afterburning chamber at temperature higher than 850–900 °C was sufficient to keep organic micropollutants concentrations in the untreated flue gas at reasonably low levels. No significant correlation of the operating conditions with emissions at the stack was found. High copper concentration in the feed enhanced PCDD/F formation, with exception of tests carried out with high afterburning temperature. The homologue profile of PCDD/F and PAH depended on test conditions. Preferential accumulation of heavy metals in the filter ash with respect to cyclone ash was quantified in terms of an enrichment factor. Out of the seven metals considered, only Cd and Pb undergo significant enrichment in the filter ash. The enrichment increased with increasing chlorine content of the feed. In contrast, Cu, Cr, Mn, Ni, and Zn behaved as refractory (non-volatile) elements even at high chlorine dosage. In accordance with the widely accepted hypothesis that metal enrichment is due to metal vaporization in the combustion chamber and subsequent condensation onto the filter ash particles, a thermodynamic model of the combustion process was able to satisfactorily predict the different metal behavior and the effect of chlorine dosage on metal enrichment.