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1.
The dissociation kinetics of the europium(III) complex with H8dotp ligand was studied by means of molecular absorption spectroscopy in UV region at ionic strength 3.0 mol dm−3 (Na,H)ClO4 and in temperature region 25-60 °C. Time-resolved laser-induced fluorescence spectroscopy (TRLIFS) was employed in order to determine the number of water molecules in the first coordination sphere of the europium(III) reaction intermediates and the final products. This technique was also utilized to deduce the composition of reaction intermediates in course of dissociation reaction simultaneously with calculation of rate constants and it demonstrates the elucidation of intimate reaction mechanism. The thermodynamic parameters for the formation of kinetic intermediate (ΔH0 = 11 ± 3 kJ mol−1, ΔS0 = 41 ± 11 J K−1 mol−1) and the activation parameters (Ea = 69 ± 8 kJ mol−1, ΔH = 67 ± 8 kJ mol−1, ΔS = −83 ± 24 J K−1 mol−1) for the rate-determining step describing the complex dissociation were determined. The mechanism of proton-assisted reaction was proposed on the basis of the experimental data.  相似文献   

2.
This study investigated the absorption of arsenic (As), sulfur (S), and phosphorus (P) in the desert plant Chilopsis linearis (Desert willow). A comparison between an inbred line (red flowered) and wild type (white flowered) plants was performed to look for differential responses to As treatment. One month old seedlings were treated for 7 days with arsenate (As2O5, AsV) at 0, 20, and 40 mg AsV L−1. Results from the ICP-OES analysis showed that at 20 mg AsV L−1, red flowered plants had 280 ± 11 and 98 ± 7 mg As kg−1 dry wt in roots and stems, respectively, while white flowered plants had 196 ± 30 and 103 ± 13 mg As kg−1 dry wt for roots and stems. At this treatment level, the concentration of As in leaves was below detection limits for both plants. In red flowered plants treated with 40 mg AsV L−1, As was at 290 ± 77 and 151 ± 60 mg As kg−1 in roots and stems, respectively, and not detected in leaves, whereas white flowered plants had 406 ± 36, 213 ± 12, and 177 ± 40 mg As kg−1 in roots, stems, and leaves. The concentration of S increased in all As treated plants, while the concentration of P decreased in roots and stems of both types of plants and in leaves of red flowered plants. X-ray absorption spectroscopy analyses demonstrated partial reduction of arsenate to arsenite in the form of As-(SX)3 species in both types of plants.  相似文献   

3.
4.
Kinetic studies of X exchange on [AuX4] square-planar complexes (where X=Cl and CN) were performed at acidic pH in the case of chloride system and as a function of pH for the cyanide one. Chloride NMR study (330-365 K) gives a second-order rate law on [AuCl4] with the kinetic parameters: (k2Au,Cl)298=0.56±0.03 s−1 mol−1 kg; ΔH2‡ Au,Cl=65.1±1 kJ mol−1; ΔS2‡ Au,Cl=−31.3±3 J mol−1 K−1 and ΔV2 Au,Cl=−14±2 cm3 mol−1. The variable pressure data clearly indicate the operation of an Ia or A mechanism for this exchange pathway. The proton exchange on HCN was determined by 13C NMR as a function of pH and the rate constant of the three reaction pathways involving H2O, OH and CN were determined: k0HCN,H=113±17 s−1, k1HCN,H=(2.9±0.7)×109 s−1 mol−1 kg and k2HCN,H=(0.6±0.2)×106 s−1 mol−1 kg at 298.1 K. The rate law of the cyanide exchange on [Au(CN)4] was found to be second order with the following kinetic parameters: (k2Au,CN)298=6240±85 s−1 mol−1 kg, ΔH2 Au,CN=40.0±0.8 kJ mol−1, ΔS2 Au,CN=−37.8±3 J mol−1 K−1 and ΔV2 Au,CN=+2±1 cm3 mol−1. The rate constant observed varies about nine orders of magnitude depending on the pH and HCN does not act as a nucleophile. The observed rate constant of X exchange on [AuX4] are two or three orders of magnitude faster than the Pt(II) analogue.  相似文献   

5.
Effects of biodrying process on municipal solid waste properties   总被引:1,自引:0,他引:1  
In this paper, the effect of biodrying process on municipal solid waste (MSW) properties was studied. The results obtained indicated that after 14 d, biodrying reduced the water content of waste, allowing the production of biodried waste with a net heating value (NHV) of 16,779 ± 2,074 kJ kg−1 wet weight, i.e. 41% higher than that of untreated waste. The low moisture content of the biodried material reduced, also, the potential impacts of the waste, i.e. potential self-ignition and potential odors production. Low waste impacts suggest to landfill the biodried material obtaining energy via biogas production by waste re-moistening, i.e. bioreactor. Nevertheless, results of this work indicate that biodrying process because of the partial degradation of the organic fraction contained in the waste (losses of 290 g kg−1 VS), reduced of about 28% the total producible biogas.  相似文献   

6.
Ferric human serum heme-albumin (heme-HSA) shows a peculiar nuclear magnetic relaxation dispersion (NMRD) behavior that allows to investigate structural and functional properties. Here, we report a thermodynamic analysis of NMRD profiles of heme-HSA between 20 and 60 °C to characterize its hydration. NMRD profiles, all showing two Lorentzian dispersions at 0.3 and 60 MHz, were analyzed in terms of modulation of the zero field splitting tensor for the S = 5/2 manifold. Values of correlation times for tensor fluctuation (τv) and chemical exchange of water molecules (τM) show the expected temperature dependence, with activation enthalpies of −1.94 and −2.46 ± 0.2 kJ mol−1, respectively. The cluster of water molecules located in the close proximity of the heme is progressively reduced in size by increasing the temperature, with Δ= 68 ± 28 kJ mol−1 and Δ= 200 ± 80 J mol−1 K−1. These results highlight the role of the water solvent in heme-HSA structure-function relationships.  相似文献   

7.
This study assesses the growth and morphological responses, nitrogen uptake and nutrient allocation in four aquatic macrophytes when supplied with different inorganic nitrogen treatments (1) NH4+, (2) NO3, or (3) both NH4+ and NO3. Two free-floating species (Salvinia cucullata Roxb. ex Bory and Ipomoea aquatica Forssk.) and two emergent species (Cyperus involucratus Rottb. and Vetiveria zizanioides (L.) Nash ex Small) were grown with these N treatments at equimolar concentrations (500 μM). Overall, the plants responded well to NH4+. Growth as RGR was highest in S. cucullata (0.12 ± 0.003 d−1) followed by I. aquatica (0.035 ± 0.002 d−1), C. involucratus (0.03 ± 0.002 d−1) and V. zizanioides (0.02 ± 0.003 d−1). The NH4+ uptake rate was significantly higher than the NO3 uptake rate. The free-floating species had higher nitrogen uptake rates than the emergent species. The N-uptake rate differed between plant species and seemed to be correlated to growth rate. All species had a high NO3 uptake rate when supplied with only NO3. It seems that the NO3 transporters in the plasma membrane of the root cells and nitrate reductase activity were induced by external NO3. Tissue mineral contents varied with species and tissue, but differences between treatments were generally small. We conclude, that the free-floating S. cucullata and I. aquatica are good candidate species for use in constructed wetland systems to remove N from polluted water. The rooted emergent plants can be used in subsurface flow constructed wetland systems as they grow well on any form of nitrogen and as they can develop a deep and dense root system.  相似文献   

8.
Previous estimations of nutrient mineralization in the water column by infaunal bivalves might have been overestimated because of underestimation of the uptake process by microphytobenthos in the field. We conducted field surveys of environmental conditions and quantitative sampling of Ruditapes philippinarum in a shallow lagoon system (Hichirippu Lagoon, eastern Hokkaido, Japan) in August 2006. We recorded the spatial distribution pattern and the molar ratio of dissolved inorganic nutrients to determine the limiting nutrients for microphytobenthos, to evaluate the input and output of nutrients at the entrance of the lagoon station, and to estimate potential nutrient mineralization by R. philippinarum. Our aim was to reevaluate the nutrient mineralization process by infaunal bivalve species. In this study, the mean standing stock of microphytobenthos inhabiting surface sediment (5 mm thick) on the tidal flats was 100 times higher than that of phytoplankton (1 m depth). Low N/P and high Si/N ratios (mean = 2.6 and 17.6, respectively) near the entrance of the lagoon compared to those of microphytobenthos (N:P:Si = 10.1:1:18) clearly suggest N deficiency. The flux of NH4-N coming into the lagoon was 3.4 kmolN d− 1, and the flux out was − 3.7 kmolN d− 1. Thus, assuming that there would have been no phytoplankton and microphytobenthos uptake during the day, 0.3 kmolN d− 1 of NH4-N was produced within the lagoon. However, the NH4-N mineralization rate of the clams has been estimated to be approximately 7.7 ± 6.8 kmolN d− 1. Thus, 96% (7.4 kmolN d− 1, i.e., 7.7 kmolN d− 1 minus 0.3 kmolN d− 1) of the NH4-N mineralized by the clam was consumed by microphytobenthos. In contrast, if all the NH4-N inflow (3.1 kmolN d− 1) was consumed by the microalgae before outflow, 52% (4.0 kmolN d− 1, i.e., 7.7 kmolN d− 1 minus 3.7 kmolN d− 1) of the NH4-N mineralized by the clams should have been consumed by microphytobenthos. Microphytobenthos on the tidal flats (11.3 ± 11.8 kmolN) used all of the surplus nutrients (between 4.0 and 7.4 kmolN d− 1), and the temporal division rate [=(NH4-N uptake)/(standing stock of microphytobenthos)] of microphytobenthos would have to be between 0.35 and 0.65 d− 1. Residual NH4-N (0.3 - 3.7 kmolN d− 1) was the water-column source and accounted for 12-148% of NH4-N in the water column near the entrance of the lagoon (2.5 ± 1.4 kmolN) per day. This is the first field-based observation with a quantitative evaluation of nutrient mineralization by infaunal bivalves and nutrient uptake by microphytobenthos.  相似文献   

9.
Population density, nitrate turnover, and oxygen respiration of benthic foraminiferans were investigated in the oxygen minimum zone (OMZ) off the Chilean coast. Live foraminiferans were found predominantly in the upper 3 mm of the sediment, and the nitrate accumulating species Nonionella cf. stella and Stainforthia sp. dominated with a combined standing stock of 2.0 × 106 Rose Bengal stained specimens m− 2. The rate of denitrification in cells of N. cf. stella analyzed with nitrous oxide microsensors during acetylene inhibition was 84 ± 33 pmol C individual− 1 d− 1. Multiplied with the standing stock of N. cf. stella and Stainforthia sp. this yielded a minimum benthic denitrification rate of 173 µmol N m− 2 d− 1 by foraminiferans. Foraminiferal denitrification, which seemed to account for almost all benthic denitrification at the investigated site will be overlooked by most conventional methods measuring benthic denitrification. Compared to the denitrification rates, the potential rates of nitrate accumulation and oxygen respiration by N. cf. stella were an order of magnitude higher (864 pmol N individual− 1 d− 1 and 760 ± 87 pmol C individual− 1 d− 1, respectively), which seems an adaptation to the infrequent availability of nitrate and oxygen in the sediment surface.  相似文献   

10.
Changes in photosynthetic pigment ratios showed that the Chlorophyll d-dominated oxyphotobacterium Acaryochloris marina was able to photoacclimate to different light regimes. Chl d per cell were higher in cultures grown under low irradiance and red or green light compared to those found when grown under high white light, but phycocyanin/Chl d and carotenoid/Chl d indices under the corresponding conditions were lower. Chl a, considered an accessory pigment in this organism, decreased respective to Chl d in low irradiance and low intensity non-white light sources. Blue diode PAM (Pulse Amplitude Modulation) fluorometry was able to be used to measure photosynthesis in Acaryochloris. Light response curves for Acaryochloris were created using both PAM and O2 electrode. A linear relationship was found between electron transport rate (ETR), measured using a PAM fluorometer, and oxygen evolution (net and gross photosynthesis). Gross photosynthesis and ETR were directly proportional to one another. The optimum light for white light (quartz halogen) was about 206 ± 51 μmol m− 2 s− 1 (PAR) (Photosynthetically Active Radiation), whereas for red light (red diodes) the optimum light was lower (109 ± 27 μmol m− 2 s− 1 (PAR)). The maximum mean gross photosynthetic rate of Acaryochloris was 73 ± 7 μmol mg Chl d− 1 h− 1. The gross photosynthesis/respiration ratio (Pg/R) of Acaryochloris under optimum conditions was about 4.02 ± 1.69. The implications of our findings will be discussed in relation to how photosynthesis is regulated in Acaryochloris.  相似文献   

11.
Extracellular freezing and dehydration concentrate hemolymph solutes, which can lead to cellular injury due to excessive water loss. Freeze tolerant larvae of the goldenrod gall fly, Eurosta solidaginis, may experience extreme cold and desiccation in winter. To determine whether larvae employ protective mechanisms against excessive cellular water loss we examined the effect of extracellular freezing and dehydration on hemolymph volume, and cryoprotectant and ion levels in the hemolymph. Dehydrated larvae or ones that had been frozen at −5 or −20 °C had a significantly smaller proportion of their body water as hemolymph (26.0-27.4%) compared to controls (30.5%). Even with this reduction in water content, hemolymph osmolality was similar or only slightly higher in frozen or dehydrated individuals than controls (908 mOsm kg−1), indicating these stresses led to a reduction in hemolymph solutes. Hemolymph and intracellular content of ions remained largely unchanged between treatment groups; although levels of Mg++ in the hemolymph were lower in larvae subjected to freezing (0.21 ± 0.01 μg mg−1 dry mass) compared to controls (0.29 ± 0.01 μg mg−1 dry mass), while intracellular levels of K+ were lower in groups exposed to low temperature (8.31 ± 0.21 μg mg−1 dry mass). Whole body glycerol and sorbitol content was similar among all treatment groups, averaging 432 ± 25 mOsm kg−1 and 549 ± 78 mOsm kg−1 respectively. However, larvae subjected to dehydration and freezing at −20 °C had a much lower relative amount of cryoprotectants in their hemolymph (∼35%) compared to controls (54%) suggesting these solutes moved into intracellular compartments during these stresses. The correlation between reduced hemolymph volume (i.e. increased cellular water content) and intracellular movement of cryoprotectants may represent a link between tolerance of dehydration and cold in this species.  相似文献   

12.
The reaction of [(η7-C7H7)Zr(η5-C5H5)] with two Lewis bases, tetramethylimidazolin-2-ylidene and PMe3, is reported and their stability probed via spectroscopic and theoretical methods. The strongly σ-basic N-heterocyclic carbene forms a stable adduct which has been structurally characterised, whilst the PMe3 ligand coordinates weakly to the metal centre. Variable temperature 31P NMR spectroscopy has been used to determine the activation energy for this process (ΔG = 40.5 ± 1.9 kJ mol−1). DFT calculations have been performed on both complexes and the structures discussed. In addition, the enthalpies for the formation of these compounds have been calculated [ΔH0(Zr-IMe) = −56.3 kJ mol−1; ΔH0(Zr-PMe3) = −2.3 kJ mol−1] and show that the N-heterocyclic carbene forms a thermodynamically much more stable adduct than that with PMe3.  相似文献   

13.
The effects of relative humidity and ambient temperature on evaporative heat loss were studied in 12 trials each with a group of 10 gilts with an initial BW of 61.7 kg (58.0–65.5 kg). The ambient temperature inside a respiration chamber was increased by 2 °C d−1 starting at 16 °C and ending at 32 °C. Relative humidity was set at 50%, 65% or 80% and remained constant within each trial. The animals had free access to feed and water. Skin temperature (SkinT), total heat production (HP), evaporative heat loss (EvapH), respiration rate (RR), and wallowing of the animals were recorded. SkinT was lowest at 80% relative humidity (P<0.05). For each degree Celsius rise in SkinT, wallowing increased by 0.19% (P<0.05). For each degree Celsius rise in ambient temperature, total HP decreased by 115 kJ pig−1 d−1 and EvapH increased by 290 kJ pig−1 d−1 (P<0.05). It was concluded that under constant high ambient temperature and relative humidity, the pigs clearly employ respiratory evaporation to lose heat. Wallowing showed the importance of skin EvapH with higher temperatures, especially at high relative humidity. This study shows the importance of evaporative cooling from the skin. The implication is that pigs at high ambient temperatures, especially in combination with a high relative humidity, should be able to wet themselves. For animal welfare and environmental reasons, it is important that they are able to wet their skin.  相似文献   

14.
The objective of the research was to investigate the effect of biomass loading, alkali (NaOH) concentration and pre-treatment time on the yield of glucose obtained following alkaline pre-treatment and enzymatic hydrolysis of oilseed rape (OSR) straw. A maximum glucose yield of (440.6 ± 14.9) g glucose kg−1 biomass was obtained when OSR straw was pre-treated at a biomass loading of 50 g kg−1 and an alkali concentration of 0.63 mol dm−3 NaOH for 30 min. The energy efficiency of glucose extraction (0.39 kg glucose MJ−1 consumed) was highest when OSR straw was pre-treated at a biomass loading of 50 g kg−1 and an alkali concentration of 0.63 or 0.75 mol dm−3 for 30 min. The study demonstrated alkaline pre-treatment of OSR straw is superior to acid pre-treatment in terms of glucose yield and energy efficiency.  相似文献   

15.
Reaction of the five-coordinate trigonal-bipyramidal platinum(II) complex, [Pt(pt)(pp3)](BF4) (pt = 1-propanethiolate, pp3 = tris[2-(diphenylphosphino)ethyl]phosphine), with I in chloroform gave the five-coordinate square-pyramidal complex with a dissociated terminal phosphino group and an apically coordinated iodide ion in equilibrium. The thermodynamic parameters for the equilibrium between the trigonal-bipyramidal and square-pyramidal geometries, [Pt(pt)(pp3)]+ + I ? [PtI(pt) (pp3)], and the kinetic parameters for the chemical exchange were obtained as follows: , ΔH0 = − 10 ± 2.4 kJ mol−1, ΔS0 = − 36 ± 10 J K−1 mol−1, , ΔH = 34 ± 4.7 kJ mol−1, ΔS = − 50 ± 21 J K−1 mol−1. The square-planar trinuclear platinum(II) complex was formed by bridging reaction of one of the terminal phosphino groups of trigonal-bipyramidal [PtCl(pp3)]Cl with trans-[PtCl2(NCC6H5)2] in chloroform. From these facts, ligand substitution reactions of [PtX(pp3)]+ (X = monodentate anion) are expected to proceed via an intermediate with a dissociated phosphino group. The rate constants for the chloro-ligand substitution reactions of [PtCl(pp3)]+ with Br and I in chloroform approached the respective limiting values as concentrations of the entering halide ions are increased. These kinetic results confirmed the preassociation mechanism in which the square pyramidal intermediate with a dissociated phosphino group and an apically coordinated halide ion is present in the rapid pre-equilibrium.  相似文献   

16.
The specific metabolic rate (SMR) and haemolymph osmolality (HO) of the mud crab Rhithropanopeus harrisii Gould, 1841 from Baltic brackish waters were measured at a habitat salinity of 7 psu (T = 15 °C, full air saturation) and after step-wise acclimation to a salinity range of 3-27 psu. Values of SMR at 7 psu varied between 0.40 and 3.89 J g− 1 WW h− 1 (n = 25, wet weight range 0.051-1.142 g) and were significantly (p < 0.05) related to the specimen's wet weight (WW) according to the power regression SMR = 0.94 WW 0.41 (R2 = 0.68). The SMR of females did not differ significantly (p > 0.05) from those of males. When exposed to higher salinities, the SMR of R. harrisii decreased significantly (p < 0.05) and reached a minimum value at 23 psu (0.55 ± 0.05 J g− 1 WW h− 1, n = 6). Mean haemolymph osmolality at 7 psu amounted to 581 ± 26 mOsm kg− 1 (n = 5) and was 2.9 times higher than that of the external medium. R. harrisii hyperosmoregulated its body fluids up to 24 psu (727 mOsm kg− 1) at which salinity the isosmotic point was reached.  相似文献   

17.
The kinetics of the reaction of Cr(CN)5(H2O)2− with NCS and were studied at pH 5.0 and at pH 6.3-7.0, respectively, as a function of the temperature between 25.0 and 55.0 °C, and at various ionic strengths. Anation occurs in competition with aquation of CN, with rate constants that exhibit less-than-first-order dependence on the concentration of the entering anions. The results are interpreted in terms of ligand interchange in a context of association of the two reacting anions mediated by the Na+ or Ca2+ counterions. The degree of aggregation depends mainly on the total cationic charge rather than on the ionic strength, and is ca. 2-fold larger for than for NCS. Within the associated species, is a better entering ligand than NCS by a factor of 4.5. The Cr(CN)5(NCS)3− and Cr(CN)5(N3)3− complexes were also synthesized, and the rates of aquation of NCS and were measured at pH 5.0 and between 55.0 and 80.0 °C, over the same range of ionic strengths. The ionic strength enhances the anation rates but has little effect on the aquation rates. The average activation enthalpies of the interchange step are 80 ± 3 and 76 ± 3 kJ mol−1 for entry of NCS and , respectively. Those of the corresponding aquation reactions are 94 ± 4 and 107 ± 4 kJ mol−1. Within error limits, all ΔH values are independent of the ionic strength. The results are consistent with an Id mechanism for substitution in Cr(CN)5Xz complexes.  相似文献   

18.
This work examined the energetic performance of a 6-month semi-continuous cultivation of Scenedesmus obliquus in an outdoor photobioreactor at mid-temperate latitude, without temperature control. By measuring the seasonal biomass production (mean 11.31, range 1.39-23.67 g m−2 d−1), higher heating value (22.94 kJ g−1) and solar irradiance, the mean seasonally-averaged photosynthetic efficiency (2.18%) and gross energy productivity (0.27 MJ m−2 d−1) was calculated. When comparing the solar energy conversion efficiency to the energy investment for culture circulation, significant improvements in reactor energy input must be made to make the system viable. Using the data collected to model the energetic performance of a substitute photobioreactor design, we conclude that sustainable photobioreactor cultivation of microalgae in similar temperate climates requires a short light path and low power input, only reasonably obtained by flat-panel systems. However, temperature control was not necessary for effective long-term cultivation.  相似文献   

19.
Colurella dicentra clones isolated from bay water in the Mississippi Gulf Coast were cultured with artificial seawater. Experiments were conducted to determine the effects of six algae species (Nannochloropsis oculata, Tetraselmis chuii, Chaetoceros gracilis, Rhodomonas salina, Isochrysis galbana, and Prorocentrum micans), six C. gracilis densities, and six N. oculata densities (25,000, 50,000, 100,000, 250,000, 500,000, and 1,000,000 cells ml− 1) on C. dicentra population growth. Algae type influenced rotifer production (p < 0.0001). C. gracilis treatment (9120 ± 3351SD) produced the highest number of rotifers followed by N. oculata (5760 ±2232SD). P. micans had the lowest number of rotifers, although not significantly different from numbers in T. chuii, R. salina, and I. galbana treatments (p > 0.05).The population growth rate (r) varied with algae species treatment. The highest values were recorded for C. gracilis treatment (0.22 to 0.26 d− 1), followed by N. oculata (0.21 to 0.24 d− 1), and the lowest for P. micans (− 0.19 to 0.14 d− 1). C. gracilis and N. oculata densities had significant effects (p < 0.0001) on C. dicentra population growth. The highest rotifer production was recorded at a C. gracilis density of 100,000 cells ml− 1, followed by 250,000 cells ml− 1 and 50,000 cells ml− 1. Algae densities of 500,000 cells ml− 1 and above produced the lowest rotifer numbers. Population growth rate (r) varied with C. gracilis densities. The highest values were observed for C. gracilis concentrations of 100,000 cells ml− 1 (0.17 to 0.19 d− 1), and the lowest for concentrations of 500,000 cells ml− 1 and above (− 0.19 to 0.09 d− 1). The 100,000 cells ml− 1N. oculata density gave the highest rotifer production followed by 50,000, 250,000, 25,000, and 500,000 cells ml− 1. Algae densities of 1,000,000 cells ml− 1 produced the lowest rotifer numbers. Population growth rate (r) varied with N. oculata densities, with the highest values obtained for algae densities of 100,000 cells ml− 1 (0.35 to 0.40 d− 1), and the lowest for concentrations of 1,000,000 cells ml− 1 (0.05 to 0.012 d− 1). This is the first report of C. dicentra in Mississippi Coastal waters, and perhaps the smallest marine rotifer species (93 by 49 μm) ever cultured successfully.  相似文献   

20.
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