994 resultados para NH(4)-N
Resumo:
The equatorial Pacific Ocean is the largest natural source of CO(2) to the atmosphere, and it significantly impacts the global carbon cycle. Much of the large flux of upwelled CO(2) to the atmosphere is due to incomplete use of the available nitrate (NO(3)) and low net productivity. This high-nutrient low-chlorophyll (HNLC) condition of the equatorial upwelling zone (EUZ) has been interpreted from modeling efforts to be due to low levels of silicate ( Si( OH) 4) that limit the new production of diatoms. These ideas were incorporated into an ecosystem model, CoSINE. This model predicted production by the larger phytoplankton and the picoplankton and effects on air-sea CO(2) fluxes in the Pacific Ocean. However, there were no size-fractionated rates available for verification. Here we report the first size-fractionated new and regenerated production rates (obtained with (15)N - NO(3) and (15)N - NH(4) incubations) for the EUZ with the objective of validating the conceptual basis and functioning of the CoSINE model. Specifically, the larger phytoplankton ( with cell diameters > 5 mu m) had greater rates of new production and higher f-ratios (i.e., the proportion of NO(3) to the sum of NO(3) and NH(4) uptake) than the picoplankton that had high rates of NH(4) uptake and low f-ratios. The way that the larger primary producers are regulated in the EUZ is discussed using a continuous chemostat approach. This combines control of Si(OH)(4) production by supply rate (bottom-up) and control of growth rate ( or dilution) by grazing ( top-down control).
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The equilibrium constant (K(,c)) under physiological conditions (38(DEGREES)C, 0.25 M ionic strength (I), pH 7.0) for the glycine synthase (GS) reaction (E C 2.1.2.1.0) (Equation 1) has been determined. (UNFORMATTED TABLE FOLLOWS)^ 5,10-CH(,2)-H(,4)Folate NADH NH (,4)+ CO(,2) ^ K(,c) = Eq. 1^ H(,4)Folate NAD('+) GLY ^(TABLE ENDS)^ The enzymatic instability of the GS enzyme complex itself has made it necessary to determine the overall K(,c) from the product of constants for the partial reactions of GS determined separately under the same conditions. The partial reactions are the H(,4)Folate-formaldehyde (CH(,2)(OH)(,2)) condensation reaction (Reaction 1) the K(,c) for which has been reported by this laboratory (3.0 x 10('4)), the lipoate (LipS(,2)) dehydrogenase reaction (LipDH) (Reaction 2) and the Gly-Lip^ decarboxylase reaction (Reaction 3) forming reduced lipoate (Lip(SH)(,2)), NH(,4)('+), CO(,2) and CH(,2)(OH)(,2.) (UNFORMATTED TABLE FOLLOWS)(,)^ H(,4)Fote + CH(,2)(OH)(,2) 5,10-CH(,2)-H(,4)Folate (1)^ Lip(SH)(,2) + NAD('+) LipS(,2) + NADH + H('+) (2)^ H('+) + Gly + LipS(,2) Lip(SH)(,2) + NH(,4)('+) CO(,2) + CH(,2)(OH)(,2) (3)^(TABLE ENDS)^ In this work the K(,c) for Reactions 2 and 3 are reported.^ The K(,c)' for the LipDH reaction described by other authors was reported with unexplainable conclusions regarding the pH depend- ence for the reaction. These conclusions would imply otherwise unexpected acid dissociation constants for reduced and oxidized lipoate. The pK(,a)',s for these compounds have been determined to resolve discrepancy. The conclusions are as follows: (1) The K(,c) for the LipDH reaction is 2.08 x 10('-8); (2) The pK(,a)',s for Lip(SH)(,2) are 4.77(-COOH), 9.91(-SH), 11.59(-SH); for LipS(,2) the carboxyl pK(,a)' is 4.77; (3) Contrary to previous literature, the log K(,c)' for the LipDH reaction is a linear function of the pH, a conclusion supported by the values for the dissociation constants.^ The K(,c) for Reaction 3 is the product of constants for Reactions 4-7. (UNFORMATTED TABLE FOLLOWS)^ LipSHSCH(,2)OH + H(,2)O Lip(SH)(,2) + CH(,2)(OH)(,2) (4)^ H(,2)O + LipSHSCH(,2)NH(,3)('+) LipSHSCH(,2)OH + NH(,4)('+) (5)^ LipSHSCH(,2)NH(,2) + H('+) LipSHSCH(,2)NH(,3)('+) (6)^ Gly + LipS(,2) LipSHSCH(,2)NH(,2) + CO(,2) (7)^(TABLE ENDS)^ Reactions 4-6 are non-enzymatic reactions whose constants were determined spectrophotometrically. Reaction 7 was catalyzed by the partially purified P-protein of GS with equilibrium approached from both directions. The value for K(,c) for this reaction is 8.15 x 10('-3). The combined K(,c) for Reactions 4-7 or Reaction 3 is 2.4 M.^ The overall K(,c) for the GS reaction determined by combination of values for Reactions 1-3 is 1.56 x 10('-3). ^
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After an experimental fire in steep shrub land in a temperate–humid region (north-west Spain), the effects of two post-fire stabilisation treatments (grass seeding and straw mulching) on the chemical properties of eroded sediments,and the amount of nutrients lost with them, we reevaluated relative to control burnt soil, over a period of 13 months. Total C and N concentrations, and d 13 C, indicated that sediments were mainly contributed by charred plant and litter material. The highest concentrations of extractable base cations in the sediments occurred during the first 3 months following fire, especially for Na and K. As treatments had little or no effect on nutrient concentration in sediments, differences in nutrient losses were due to the 10-fold lower sediment production in mulching compared with other treatments. In control and seeding treatments, the accumulated amounts of nutrients lost with sediments were 989–1028kgha 1 (C), 77kgha 1 (N), 1.9–2.4kgha 1 (Ca), 0.9–1.1kgha 1 (Mg), 0.48–0.55kgha 1 (NH 4 þ –N), 0.39–0.56kgha 1 (K), 0.19–0.34kgha 1 (Na) and , 0.1kgha 1 (P and NO 3 –N) . These values accounted for 22–25% (total C and N) and 5–12% (NH 4 þ –N, Ca, P and Mg) of available nutrients in ash, and 1.0–2.4% of those in ash þ topsoil. As nutrient and sediment losses were strongly correlated, the reduction of the latter by mulching application leads to an effective decrease of post-fire nutrient losses.
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The effects of fire ( Control burned soil) and two emergency stabilisation techniques (grass Seeding and straw Mulching ) on 20 chemical characteristics were evaluated on 0 – 5 cm top-soils sampled 1, 90, 180 and 365 days after an experimental fi re in a steep shrubland of a temperate-humid region (NW Spain). Most part of pH (in H 2 O and KCl) variance was explained by the sampling date. No clear temporal trends were identi fi able for total soil C and N content, likely due to the large SOM pool in these soils; however, changes on soil δ 13 C were explained by the deposition of 13 C-depleted ashes, followed by its progressive erosion, while those on soil δ 15 N were a consequence of fi re induced N outputs. After the fi re, NH 4 + – N, P, Na, K, Mg, Ca, Mn, Cu, Zn and B concentrations increased, while those of NO 3 − – N, Al, Fe and Co did not vary significantly. Despite a significant decline with time, concentrations of Mg, Ca and Mn at the end of the study were still higher than in unburned soil, while those of K, Cu, Zn and B were similar to the pre-fire levels and those of NH 4 + – N, P and Na were below pre-fire values. Mulching and Seeding treatments for burned soil emergency stabilisation had significant effects on soil δ 15 N and extractable K, Mg and Ca, while data were inconclusive for their possible effects on the extractable Al, Fe and Co
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In the Florida Everglades, tree islands are conspicuous heterogeneous elements in a complex wetland landscape. I investigated the effects of increased freshwater flow in southern Everglades seasonally flooded tree islands, and characterized biogeochemical interactions among tree islands and the marsh landscape matrix, specifically examining hydrologic flows of nitrogen (N), and landscape N sequestration capacity. I utilized ecological trajectories of key ecosystem variables to differentiate effects of increased sheetflow and hydroperiod. I utilized stable isotope analyses and nutrient content of tree island ecosystem components to test the hypothesis that key processes in tree island nitrogen cycling would favor ecosystem N sequestration. I combined estimates of tree island ecosystem N standing stocks and fluxes, soil and litter N transformation rates, and hydrologic inputs of N to quantify the net sequestration of N by a seasonally flooded tree island. ^ Results show that increased freshwater flow to seasonally flooded tree islands promoted ecosystem oligotrophy, whereas reduced flows allowed some plant species to cycle P less efficiently. As oligotrophy is a defining parameter of Everglades wetlands, and likely promotes belowground production and peat development, reintroducing freshwater flow from an upstream canal had a favorable effect on ecosystem dynamics of tree islands in the study area. Important factors influencing the stable isotopic composition of nitrogen and carbon were: (1) a contribution to soil N by soil invertebrates, animal excrement, and microbes, (2) a possible NO3 source from an upstream canal and an "open" ecosystem N cycle, and (3) greater availability of phosphorus in tree islands relative to the marsh landscape, suggesting that tree island N cycling favors N sequestration. Hydrologic sources of N were dominated by surface water loads of NO3- and NH 4+, and an important soil N transformation promoting the net loss of surface water DIN was nitrate immobilization associated with soils and surficial leaf litter. The net inorganic N sequestration capacity of a seasonally flooded tree island was 50 g yr-1 m -2. Thus, tree islands likely have an important function in landscape sequestration of inorganic N, and may reduce significant anthropogenic N loads to downstream coastal systems. ^
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A multivariate statistical analysis was applied to a 10 year, multiparameter data set in an effort to describe the spatial dependence and inherent variation of water quality patterns in the mangrove estuaries of Ten Thousand Islands – Whitewater Bay area. Principal component analysis (PCA) of 16 water quality parameters collected monthly resulted in five groupings, which explained 72.5% of the variance of the original variables. The “Organic” component (PCI) was composed of alkaline phosphatase activity, total organic nitrogen, and total organic carbon; the “Dissolved Inorganic N” component (PCII) contained NO 3 − , NO 2 − , and NH 4 + ; the “Phytoplankton” component (PCIII) was made up of total phosphorus, chlorophyll a, and turbidity; dissolved oxygen and temperature were inversely related (PCIV); and salinity and soluble reactive phosphorus made up PCV. A cluster analysis of the mean and SD of PC scores resulted in the spatial aggregation of the 47 fixed stations into six classes having similar water quality, which we defined as: Mangrove Rivers, Whitewater Bay, Gulf Islands, Coot Bay, Blackwater River, and Inland Waterway. Marked differences in physical, chemical, and biological characteristics among classes were illustrated by this technique. Comparison of medians and variability of parameters among classes allowed large scale generalizations as to underlying differences in water quality in these regions. A strong south to north gradient in estuaries from high N - low P to low N - high P was ascribed to marked differences in landuse, freshwater input, geomorphology, and sedimentary geology along this tract. The ecological significance of this gradient discussed along with potential effects of future restoration plans.
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Long-term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on Florida Bay biogeochemistry. Planktonic communities respond quickly to changes in water quality, thus spatial variability in community composition and relationships to nutrient parameters must be understood in order to evaluate future downstream impacts of modifications to Everglades hydrology. Here we present initial results combining flow cytometry analyses of phytoplankton and bacterial populations (0.1–50 μm size fraction) with measurements of δ13C and δ15N composition and dissolved inorganic nutrient concentrations to explore proxies for planktonic species assemblage compositions and nutrient cycling. Particulate organic material in the 0.1–50 μm size fraction was collected from five stations in Northeastern and Western Florida Bay to characterize spatial variability in species assemblage and stable isotopic composition. A dense bloom of the picocyanobacterium, Synechococcus elongatus, was observed at Western Florida Bay sites. Smaller Synechococcus sp. were present at Northeast sites in much lower abundance. Bacteria and detrital particles were also more abundant at Western Florida Bay stations than in the northeast region. The highest abundance of detritus occurred at Trout Creek, which receives freshwater discharge from the Everglades through Taylor Slough. In terms of nutrient availability and stable isotopic values, the S. elongatus population in the Western bay corresponded to low DIN (0.5 μM NH 4 + ; 0.2 μM NO 3 − ) concentrations and depleted δ15N signatures ranging from +0.3 to +0.8‰, suggesting that the bloom supported high productivity levels through N2-fixation. δ15N values from the Northeast bay were more enriched (+2.0 to +3.0‰), characteristic of N-recycling. δ13C values were similar for all marine Florida Bay stations, ranging from −17.6 to −14.4‰, however were more depleted at the mangrove ecotone station (−25.5 to −22.3‰). The difference in the isotopic values reflects differences in carbon sources. These findings imply that variations in resource availability and nutrient sources exert significant control over planktonic community composition, which is reflected by stable isotopic signatures.
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The need to preserve the environment has led to the search for new materials for efficient disposal of chemical compounds that alter the stability of our natural resources. Among these resources, stands in first place the water, as a precious commodity and scarce, leading to the proper use and reuse. As a result, the World Health Organization has established maximum permissible values in drinking water, such as: 50 mg/L, 0, 1 mg/L and 0, 5 mg/L to at-3, at-2, NH 4, respectively. For these reasons, assesses the implementation of new materials and water treatment processes aiming at the removal of these compounds, such as alumina, in the form of powder or as a support for a catalytic system using inorganic membranes capable of supporting more severe conditions of temperature and pressure by opening new possibilities for applications of membrane reactors; and also for electrochemical treatments with doped diamond bobo electrodes (BDD) as anode and copper as cathode. For such purpose, was conducted the study of adsorption of nitrate in different times to assess the time required to achieve equilibrium by employing three commercial alumina called: acidic, basic and neutral alumina, with subsequent treatment only in the acidic alumina impregnating metals (PdCu/Al2O3) for the catalytic reaction. The materials were previously characterized by XRD, SEM techniques and ABET. Aluminas presented a considerable adsortive capacity of nitrate in the first thirty minutes, equivalent to 50% of removal reaching equilibrium in that time. After treatment, using alumina as catalyst for the reaction in batch reactor (Pd-Cu/Al2O3), the results were more favourable, totalling 64% reduction of ion NO3-at the end of three hours. On the other hand, the results for the catalytic reaction using the catalytic support Pd-Cu/TiO2 in membrane reactor proved to be low. -if, in this way, improve the conditions of catalytic system to optimize the process. Already, for the electrochemical tests using DDB1 electrodes as anode, and Cu, as cathode, there was a fairly significant nitrate reduction, approximately 80% of ion removal during three hours and cost viable applications.
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This paper provides a method for constructing a new historical global nitrogen fertilizer application map (0.5° × 0.5° resolution) for the period 1961-2010 based on country-specific information from Food and Agriculture Organization statistics (FAOSTAT) and various global datasets. This new map incorporates the fraction of NH+4 (and NONO-3) in N fertilizer inputs by utilizing fertilizer species information in FAOSTAT, in which species can be categorized as NH+4 and/or NO-3-forming N fertilizers. During data processing, we applied a statistical data imputation method for the missing data (19 % of national N fertilizer consumption) in FAOSTAT. The multiple imputation method enabled us to fill gaps in the time-series data using plausible values using covariates information (year, population, GDP, and crop area). After the imputation, we downscaled the national consumption data to a gridded cropland map. Also, we applied the multiple imputation method to the available chemical fertilizer species consumption, allowing for the estimation of the NH+4/NO-3 ratio in national fertilizer consumption. In this study, the synthetic N fertilizer inputs in 2000 showed a general consistency with the existing N fertilizer map (Potter et al., 2010, doi:10.1175/2009EI288.1) in relation to the ranges of N fertilizer inputs. Globally, the estimated N fertilizer inputs based on the sum of filled data increased from 15 Tg-N to 110 Tg-N during 1961-2010. On the other hand, the global NO-3 input started to decline after the late 1980s and the fraction of NO-3 in global N fertilizer decreased consistently from 35 % to 13 % over a 50-year period. NH+4 based fertilizers are dominant in most countries; however, the NH+4/NO-3 ratio in N fertilizer inputs shows clear differences temporally and geographically. This new map can be utilized as an input data to global model studies and bring new insights for the assessment of historical terrestrial N cycling changes.
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Distributions of pore water O2, NO-2, NO-3, NH+4, Si(OH)4, PO[3-]4, Mn[2+], F-, and T.A. were determined at 15 stations in the eastern equatorial Atlantic. While overall profile characteristics are consistent with previous models of organic matter diagenesis, profile shapes suggest that a deep reaction layer, rich in organic C, is also present at many sites. While it is unlikely that the oxidation of organic C in this layer has had a major effect on the ocean C cycle, pore water profile shapes are significantly altered. Despite exposure to seawater SO[2-]4 concentrations for > 1000 years, decomposition of the organic matter in the layer appears to be restricted to oxic and suboxic processes. These results suggest major differences in organic carbon decomposition and preservation under oxic/suboxic and anoxic conditions. Present-day benthic fluxes are largest adjacent to the eastern boundary coastal upwelling region and similar in magnitude to values reported for the eastern Pacific. Preliminary estimates suggest that the benthic respiration in the eastern 1/3 of the North Atlantic south of 20°N may alone account for >20% of the total deep North Atlantic respiration. Combining these results with estimates of organic C burial and deep water-column decomposition suggests that this region is a major location of organic C input into the deep sea.
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Effects of fire on biogeochemical cycling in terrestrial ecosystem are widely acknowledged, while few studies have focused on the bacterial community under the disturbance of long-term frequent prescribed fire. In this study, three treatments (burning every two years (B2), burning every four years (B4) and no burning (B0)) were applied for 38 years in an Australian wet sclerophyll forest. Results showed that bacterial alpha diversity (i.e. bacterial OTU) in the top soil (0-10 cm) was significantly higher in the B2 treatment compared with the B0 and B4 treatments. Non-metric multidimensional analysis (NMDS) of bacterial community showed clear separation of the soil bacterial community structure among different fire frequency regimes and between the depths. Different frequency fire did not have a substantial effect on bacterial composition at phylum level or bacterial 16S rRNA gene abundance. Soil pH and C:N ratio were the major drivers for bacterial community structure in the most frequent fire treatment (B2), while other factors (EC, DOC, DON, MBC, NH 4 +, TC and TN) were significant in the less frequent burning and no burning treatments (B4 and B0). This study suggested that burning had a dramatic impact on bacterial diversity but not abundance with more frequent fire.
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We present the results of isotope measurements (δ 18 O, δ D, δ 13 C DIC and 14 C) and chemical analyses (TDS, TOC, HCO 3– , SO 42– , Cl – , NO 3– , NH 4+ , Ca 2+ , Mg 2+ Na + and K + ) conducted on groundwater samples collected from deep Cenozoic aqui- fers. These aquifers are the basic source of drinking water at numerous localities within the study area in northern Po- land. Most of the δ 18 O determinations are characterised by low variability (i.e., > 70 per cent of δ 18 O are between –9.5‰ and –9.2‰). In most cases tritium activity was not detected or its content slightly exceeded the uncertainty of measure- ment (from ±0.3 T.U. to ± 0.5 T.U.). On average, 14 C activity is twice higher than that under similar conditions and in hydrogeological systems. The δ 13 C DIC values fall within the –13.6‰ to –12.8‰ range. A slight variability is observed when considering all isotope and chemical data within the study area and under these hydrogeological conditions. In general, the results of isotope and chemical analyses seem to be homogeneous, indicating the presence of closely similar groundwaters in the system, irrespective of geological formation. It is likely that there is a significant hydraulic connec- tion between shallow and deep aquifers in the Gwda catchment, which indicates the potential for seepage of pollutants from shallow Pleistocene to deep Miocene aquifers. This can endanger the latter by e.g., high concentrations of NO 3– , SO 42– and Cl – ions from shallow aquifers within the Gwda catchment.
Resumo:
Two novel compounds, [Co(4,4'-bipy)(H2O)(4)](4-abS)(2).H2O (1) and [Mn(4,4'-bipy)(H2O)(4)](4-abs)(2).2H(2)O (2) (4,4'-bipy = 4,4'-bipyridine; 4-abs = 4-aminobenzenesulfonate), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses, UV-vis and IR spectra, and TG analysis. X-ray structural analysis revealed that 1 and 2 both possess unusual hydrogen-bonded three-dimensional (3-D) networks encapsulating one-dimensional (1-D) covalently bonded infinite [M(4,4'-bipy)(H2O)(4)](2+) (M = Co, Mn) chains. The 4-abs anions in 1 form 1-D zigzag chains through hydrogen bonds. These chains are further extended through crystallization water molecules into 3-D hydrogen-bonded networks with 1-D channels, in which the [Co(4,4'-bipy)(H2O)(4)](2+) linear covalently bonded chains are located. Crystal data for 1: C22H30CoN4O11S2, monoclinic P2(1), a = 11.380(2) Angstrom, b = 8.0274(16) Angstrom, c = 15.670(3) Angstrom, alpha = gamma = 90degrees, beta = 92.82(3)degrees, Z = 2. Compound 2 contains interesting two-dimensional (2-D) honeycomb-like networks formed by 4-abs anions and lattice water molecules via hydrogen bonding, which are extended through other crystallization water molecules into three dimensions with 1-D hexagonal channels. The [Mn(4,4'-bipy)(H2O)(4)](2+) linear covalent chains exist in these channels. Crystal data for 2: C22H32WN4O12S2, monoclinic P2(1)/c, a = 15.0833(14) Angstrom, b = 8.2887(4) Angstrom, c = 23.2228(15) Angstrom, alpha = gamma = 90degrees, beta = 95.186(3)degrees, Z = 4.
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The ""Ru(P-P)"" unit (P-P = diphosphine) is recognized to be an important core in catalytic species for hydrogenation of unsaturated organic substrates. Thus, in this study we synthesized six new complexes containing this core, including the binuclear complex [(dppb)(CO)Cl(2)Ru-pz-RuCl(2)(CO)(dPPb)] (pz = pyrazine) which can be used as a precursor for the synthesis of cationic carbonyl species of general formula [RuCl(CO)(dppb)(N-N)]PF(6) (N-N = diimine). Complexes with the formula (RuCl(py)(dppb)(N-N)]PF(6) were synthesized by exhaustive electrolysis of these carbonyl compounds or from the precursors [RuCl(2)(dppb)(N-N)]. The new complexes were characterized by microanalysis, conductivity measurements, IR and (31)P{(1)H)} NMR spectroscopy, cyclic voltammetry and X-ray crystallography. (C) 2010 Elsevier Ltd. All rights reserved.
Resumo:
The modification of a gold electrode surface by electropolymerization of trans-[Ru(NH(3))(4)(Ist)SO(4)](+) to produce an electrochemical sensor for nitric oxide was investigated. The influence of dopamine, serotonin and nitrite as interferents for NO detection was also examined using square-wave voltammetry (SWV). The characterization of the modified electrode was carried out by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) and SERS techniques. The gold electrode was successfully modified by the trans-[Ru(NH(3))(4)(Ist)SO(4)](+) complex ion using cyclic voltammetry. The experiments show that a monolayer of the film is achieved after ten voltammetric cycles, that NO in solution can coordinate to the metal present in the layer, that dopamine, serotonin and nitrite are interferents for the detection of NO, and that the response for the nitrite is much less significant than the responses for dopamine and serotonin. The proposed modified electrode has the potential to be applied as a sensor for NO. (C) 2011 Elsevier Ltd. All rights reserved.