Abstract  Abstract Aims: Inorganic nitrate and nitrite from endogenous and dietary sources have emerged as alternative substrates for nitric oxide (NO) formation in addition to the classic L-arginine NO synthase (NOS)-dependent pathway. Here, we investigated a potential cross-talk between these two pathways in the regulation of vascular function. Results: Long-term dietary supplementation with sodium nitrate (0.1 and 1 mmol kg(-1) day(-1)) in rats caused a reversible dose-dependent reduction in phosphorylated endothelial NOS (eNOS) (Ser1177) in aorta and a concomitant increase in phosphorylation at Thr495. Moreover, eNOS-dependent vascular responses were attenuated in vessels harvested from nitrate-treated mice or when nitrite was acutely added to control vessels. The citrulline-to-arginine ratio in plasma, as a measure of eNOS activity, was reduced in nitrate-treated rodents. Telemetry measurements revealed that a low dietary nitrate dose reduced blood pressure, whereas a higher dose was associated with a paradoxical elevation. Finally, plasma cyclic guanosine monophosphate increased in mice that were treated with a low dietary nitrate dose and decreased with a higher dose. Innovation and Conclusions: These results demonstrate the existence of a cross-talk between the nitrate-nitrite-NO pathway and the NOS-dependent pathway in control of vascular NO homeostasis. Antioxid. Redox Signal. 00, 000-000.

Abstract  New cationic silver-containing ionic liquids were synthesized and used as non-aqueous electrolytes for the electrodeposition of silver layers. In the liquid state of these ionic liquids, a silver (i) cation is coordinated by pyridine-N-oxide (py-O) ligands in a 1 : 3 metal-to-ligand ratio, although in some cases a different stoichiometry of the silver center crystallized out. As anions, bis(trifluoromethanesulfonyl)imide (Tf2N), trifluoromethanesulfonate (OTf), methanesulfonate (OMs) and nitrate were used, yielding compounds with the formulae [Ag(py-O)3][Tf2N], [Ag(py-O)3][OTf], [Ag(py-O)3][OMs] and [Ag(py-O)3][NO3], respectively. The compounds were characterized by CHN analysis, FTIR, NMR, DSC, TGA and the electrodeposition of silver was investigated by cyclic voltammetry, linear potential scans, scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDX). With the exception of [Ag(py-O)3][Tf2N], which melts at 108 °C, all the silver(i) compounds have a melting point below 80 °C and were tested as electrolytes for silver electrodeposition. Interestingly, very high current densities were observed at a potential of -0.5 V vs. Ag/Ag(+) for the compounds with fluorine-free anions, i.e. [Ag(py-O)3][NO3] (current density of -10 A dm(-2)) and [Ag(py-O)3][OMs] (-6.5 A dm(-2)). The maximum current density of the compound with the fluorinated anion trifluoromethanesulfonate, [Ag(py-O)3][OTf], was much lower: -2.5 A dm(-2) at -0.5 V vs. Ag/Ag(+). Addition of an excess of ligand to [Ag(py-O)3][OTf] resulted in the formation of the room-temperature ionic liquid [Ag(py-O)6][OTf]. A current density of -5 A dm(-2) was observed at -0.5 V vs. Ag/Ag(+) for this low viscous silver salt. The crystal structures of several silver complexes could be determined by X-ray diffraction, and it was found that several of them had a stoichiometry different from the 1 : 3 metal-to-ligand ratio used in their synthesis. This indicates that the compounds form crystals with a composition different from that of the molten state. The electrochemical properties were measured in the liquid state, where the metal-to-ligand ratio was 1 : 3. Single crystal X-ray diffraction measurements showed that silver(i) is six coordinate in [Ag(py-O)3][Tf2N] and [Ag(py-O)3][OTf], while it is five coordinate in the other complexes. In [Ag3(py-O)8][OTf]3, there are two different coordination environments for silver ions: six coordinate central silver ions and five coordinate for the outer silver ions. In some of the silver(i) complexes, silver-silver interactions were observed in the solid state.

Abstract  OBJECTIVES: Mustard is highly toxic to the lung. Its toxic effects are associated with inflammatory cell accumulation and increased pro-inflammatory cytokines as well as reactive oxygen and nitrogen species. In this study, we aimed to investigate the efficiency of melatonin (MEL) and S-methylisothiourea (SMT) on mechlorethamine (MEC) induced lung toxicity.

METHODS: Thirty-six male rats were randomly divided into four groups: control, MEC, MEC+MEL, and MEC+SMT. Control group was given saline only via transdermal route. Other groups were exposured to a single dose of MEC (3.5 mg/kg) via transdermal route. MEL (100 mg/kg) was administered intraperitoneally 30 min after the application of MEC, and after the same dose of MEL was given every 12 h for a total of six doses. SMT (50 mg/kg) was also given intraperitoneally 30 min after the application of MEC.

RESULTS: MEC injection resulted in alveolar epithelial injury, hemorrhage, inflammation, edema and interalveolar septal thickening in the lung tissues. The tissue TNF-α, IL-1β, and nitrate/nitrite (NOx) levels were found significantly different for all groups (p<0.001). TNF-α and IL-1β levels increased significantly with MEC exposure, and MEL and SMT ameliorated these increases in lung tissues. MEC also elevated NOx levels in lung tissue. Melatonin showed meaningful protection against lung injury. But protection of SMT was weaker.

CONCLUSION: Inflammation plays an important role in the MEC induced lung toxicity as well as oxidative and nitrosative stress. Melatonin has also anti-inflammatory properties similar to SMT, as well as anti-oxidant properties. But melatonin treatment was found more efficient than SMT treatment.

Abstract  We described the preparation of a novel nanobiocomposite, reduced graphene oxide- multiwalled carbon nanotubes-platinum nanoparticles/myoglobin (RGO-MWCNT-Pt/Mb) for the direct electrochemistry of myoglobin and its application towards determination of hydrogen peroxide (H2O2) and nitrite (NO2(-)). RGO-MWCNT-Pt nanocomposite has been prepared by simple solution based approach and its structure was characterized. RGO-MWCNT-Pt/Mb nanobiocomposite was prepared and attained the direct electrochemistry of Mb with pair of well-defined redox peaks with the formal potential of -0.33 V and peak to peak separation of 22 mV. Amount of electroactive protein (Г) and heterogeneous electron transfer rate constant (ks) were calculated to be 1.04 × 10 (-9) mol cm(-2) and 9.47 s(-1). The sensor displayed lowest detection limit (LOD) of 6 pM which is the lowest LOD ever achieved for the detection of H2O2. Two linear ranges were observed for the detection of H2O2: (1) 10 pM-0.19 nM with sensitivity of 1.99 (± 0.058) µA pM(-1)cm(-2) and (2) 0.25 nM-2.24 µM with sensitivity of 0.037 (± 0.081) µA nM(-1)cm(-2). In addition, the biosensor offered good analytical parameters towards determination of NO2(-) with wide linear range of 1 µM to 12 mM and high sensitivity of 0.1651 (± 0.026) µA µM(-1) cm(-2). The sensor acquires good selectivity, repeatability, reproducibility and stability. The practical feasibility of the sensor has been addressed.

Abstract  Under autotrophic conditions, we investigated the effects of different current densities on bioelectrochemical denitrification (BED). In this study, nitrate consumption and nitrous oxide (N2O) production, microbial diversity and population dynamics, and denitrification pathway gene expressions were explored in continuous flow BED reactors at different current densities (0.2, 1, 5, 10 and 20 A/m(2)). We found that, under the autotrophic conditions, N2O accumulation was increased with increase in current density. The maximum rate of denitrification was 1.65 NO3(-)-N (g/NCCm(3).h), and approximately 70% of the reduced N was accumulated as N2O. After each current density was applied, pyrosequencing of the expressed 16S rRNA genes amplified from the cathodic biofilms revealed that that 16 genera were active and in common at all currents, and that eight of those showed a statistically significant correlation with particular current densities. The relative expression of napA and narG was highest, whereas nosZ was low relative to its level in the inoculum suggesting that this could have contributed the high N2O accumulation. Kinetic analysis of nitrate reduction and N2O accumulation followed Michaelis-Menten kinetics. The Vmax for nitrate consumption and N2O accumulation were similar, however the Km values determined as A/m(2) were not. This study provides better understanding of the community and kinetics of a current-fed, autotrophic, cathodic biofilm for evaluating its potential for scale-up and for N2O recovery.

Abstract  Five metal complexes of 2-methylisothiazol-3(2H)-one (MIO), [Co(III)(NH3)5(MIO)](3+), [Ru(II)(NH3)5(MIO)](2+), [Ru(III)(NH3)5(MIO)](3+), [Pt(II)Cl3(MIO)](-), and trans-[U(VI)O2(NO3)2(MIO)2], were synthesized, and their structures were determined by single-crystal X-ray crystallography. MIO is an ambidentate ligand and coordinates to metal centers through its oxygen atom in the cobalt(III), ruthenium(III), and uranium(VI) complexes and through its sulfur atom in the ruthenium(II) and platinum(III) complexes. This result suggests that MIO shows preferential behavior on its donating atoms. We also studied the electron-donor abilities of the oxygen and sulfur atoms of MIO. Various physical measurements on the conjugate acid of MIO and the MIO complexes allowed us to determine an acid dissociation constant (pKa) and donor number (DN) for the oxygen atom of MIO and Lever's electrochemical parameter (EL) and a relative covalency parameter (kL) for the sulfur atom.

Abstract  The anti-inflammatory activity of eriodictyol and its mode of action were investigated. Eriodictyol suppressed tumor necrosis factor (mTNF)-α, inducible nitric oxide synthase (miNOS), interleukin (mIL)-6, macrophage inflammatory protein (mMIP)-1, and mMIP-2 cytokine release in LPS-stimulated macrophages. We found that the anti-inflammatory cascade of eriodictyol is mediated through the Toll-like Receptor (TLR)4/CD14, p38 mitogen-activated protein kinases (MAPK), extracellular-signal-regulated kinase (ERK), Jun-N terminal kinase (JNK), and cyclooxygenase (COX)-2 pathway. Fluorescence quenching and saturation-transfer difference (STD) NMR experiments showed that eriodictyol exhibits good binding affinity to JNK, 8.79 × 10(5) M(-1). Based on a docking study, we propose a model of eriodictyol and JNK binding, in which eriodictyol forms 3 hydrogen bonds with the side chains of Lys55, Met111, and Asp169 in JNK, and in which the hydroxyl groups of the B ring play key roles in binding interactions with JNK. Therefore, eriodictyol may be a potent anti-inflammatory inhibitor of JNK.

Abstract  Nitrogen (N) isotope ratios ((15)N/(14)N) provide integrative constraints on the N inventory of the modern ocean. Anaerobic ammonium oxidation (anammox), which converts ammonium and nitrite to dinitrogen gas (N2) and nitrate, is an important fixed N sink in marine ecosystems. We studied the so far unknown N isotope effects of anammox in batch culture experiments. Anammox preferentially removes (14)N from the ammonium pool with an isotope effect of +23.5‰ to +29.1‰, depending on factors controlling reversibility. The N isotope effects during the conversion of nitrite to N2 and nitrate are (i) inverse kinetic N isotope fractionation associated with the oxidation of nitrite to nitrate (-31.1 ± 3.9‰), (ii) normal kinetic N isotope fractionation during the reduction of nitrite to N2 (+16.0 ± 4.5‰), and (iii) an equilibrium N isotope effect between nitrate and nitrite (-60.5 ± 1.0‰), induced when anammox is exposed to environmental stress, leading to the superposition of N isotope exchange effects upon kinetic N isotope fractionation. Our findings indicate that anammox may be responsible for the unresolved large N isotope offsets between nitrate and nitrite in oceanic oxygen minimum zones. Irrespective of the extent of N isotope exchange between nitrate and nitrite, N removed from the combined nitrite and nitrate (NOx) pool is depleted in (15)N relative to NOx. This net N isotope effect by anammox is superimposed on the N isotope fractionation by the co-occurring reduction of nitrate to nitrite in suboxic waters, possibly enhancing the overall N isotope effect for N loss from oxygen minimum zones.

Abstract  Several papers reported associations between airborne fine particulate matter (PM2.5) and birth weight, though findings are inconsistent across studies. Conflicting results might be due to (1) different PM2.5 chemical structure across locations, and (2) various exposure assignment methods across studies even among the studies that use ambient monitors to assess exposure. We investigated associations between birth weight and PM2.5 chemical constituents, considering issues arising from choice of buffer size (i.e. distance between residence and pollution monitor). We estimated the association between each pollutant and term birth weight applying buffers of 5 to 30 km in Connecticut (2000-2006), in the New England region of the USA. We also investigated the implication of the choice of buffer size in relation to population characteristics, such as socioeconomic status. Results indicate that some PM2.5 chemical constituents, such as nitrate, are associated with lower birth weight and appear more harmful than other constituents. However, associations vary with buffer size and the implications of different buffer sizes may differ by pollutant. A homogeneous pollutant level within a certain distance is a common assumption in many environmental epidemiology studies, but the validity of this assumption may vary by pollutant. Furthermore, we found that areas close to monitors reflect more minority and lower socio-economic populations, which implies that different exposure approaches may result in different types of study populations. Our findings demonstrate that choosing an exposure method involves key tradeoffs of the impacts of exposure misclassification, sample size, and population characteristics.

Abstract  Concentrations of heme b, the iron-containing component of b-type hemoproteins, ranged from<0.4 to 5.3 pM with an average of 1.180.8 pM ( 1 sigma; n=86) in the Iceland Basin (IB), from<0.4 to 19.1 pM with an average of 2.241.67 pM (n=269) in the tropical northeast Atlantic (TNA) and from 0.6 to 21 pM with an average of 5.14.8 pM (n=34) in the Scotia Sea (SS). Heme b concentrations were enhanced in the photic zone and decreased with depth. Heme b concentrations correlated positively with chlorophyll a (chl a) in the TNA (r=0.41, p<0.01, n=269). Heme b did not correlate with chl a in the IB or SS. In the IB and SS, stations with high-chlorophyll and low-nutrient (Fe and/or Si) concentrations exhibited low heme b concentrations relative to particulate organic carbon (< 0.1molmol(-1)), and high chl a:heme b ratios (> 500). High chl a:heme b ratios resulted from relative decreases in heme b, suggesting proteins such as cytochrome b(6)f, the core complex of photosystem II, and eukaryotic nitrate reductase were depleted relative to proteins containing chlorophyll such as the eukaryotic light-harvesting antenna. Relative variations in heme b, particulate organic carbon, and chl a can thus be indicative of a physiological response of the phytoplankton community to the prevailing growth conditions, within the context of large-scale changes in phytoplankton community composition.

Abstract  The effectiveness of measures to mitigate nitrate concentrations in surface and groundwater depends not only on their suitability for reducing nitrate leaching, but also on characteristics of groundwater transport that may cause a lag in achieving recovery. The recovery of a catchment within a Nitrate Vulnerable Zone in the east of Scotland has been assessed using a combined monitoring and modelling approach. Understanding of the dominant hydrological processes was developed through a programme of monitoring of surface and groundwater bodies. Age dating of groundwater samples, using dissolved atmospheric trace gases (CFCs and SF6) underpinned the conceptualisation of groundwater transport and a lumped dispersion model was applied to the data to estimate mean solute transit times. High spatial variability in the groundwater dating made it difficult to estimate catchment means, but the range was estimated to lie between 15 and 60 years. A catchment hydrology and nitrate model was used to explore the effect of simple changes in land management on reducing nitrate concentrations, as well as associated time scales of recovery. The study has helped improve understanding of the role of groundwater in catchment recovery and given an indication of the scale of agricultural changes required to achieve different levels of pollution mitigation.

Abstract  Nanocrystalline Cu3B2O6 particles were produced by ultrasonic spray pyrolysis (USP) method using aqueous solution of copper nitrate and boric acid in desired concentration. Particles obtained thermal decomposition of precursor under constant air flow rate at 1000 degrees C furnace temperature. Then samples were structurally characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). The results show that nanocrystalline Cu3B2O6 particles in nearly spherical morphology were prepared successfully. Also, XRD analysis reveal that obtained Cu3B2O6 particles have anorthic crystal structure and their crystalline size are nearly 29 nm, which are calculated by Scherrer equation.

Abstract  The nanocrystalline LiFexMn(2-x)O(4) (x=0.2-1.0) particles were prepared by ultrasonic spray pyrolysis method using nitrate salts of ingredients at 800 degrees C in air atmosphere. Particle properties were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy. Besides, cyclic voltammetry and galvanostatic tests were performed to investigate the effects of the iron substituent amount on electrochemical behavior. Particle characterization studies show that nanocrystalline particles have spinel structure and they are in submicron size range with spherical morphology. The lowest iron doped sample (LiFe0.2Mn1.8O4) exhibits 117 mAh g(-1) cumulative discharge capacity at 0.5C and 88% capacity retention for 4 V plateau after 50 cycles. At higher iron concentrations, substituent tends to occupy the 8a tetrahedral sites, which prevent the lithium transport in the lattice during charge-discharge process. Increasing of the iron amount in the spinet structure causes the deterioration of the electrochemical performance. (C) 2012 Elsevier Ltd. All rights reserved.

Abstract  A soil bacterium capable of utilizing methyl parathion as sole carbon and energy source was isolated by selective enrichment on minimal medium containing methyl parathion. The strain was identified as belonging to the genus Serratia based on a phylogram constructed using the complete sequence of the 16S rRNA. Serratia sp. strain DS001 utilized methyl parathion, p-nitrophenol, 4-nitrocatechol, and 1,2,4-benzenetriol as sole carbon and energy sources but could not grow using hydroquinone as a source of carbon. p-Nitrophenol and dimethylthiophosphoric acid were found to be the major degradation products of methyl parathion. Growth on p-nitrophenol led to release of stoichiometric amounts of nitrite and to the formation of 4-nitrocatechol and benzenetriol. When these catabolic intermediates of p-nitrophenol were added to resting cells of Serratia sp. strain DS001 oxygen consumption was detected whereas no oxygen consumption was apparent when hydroquinone was added to the resting cells suggesting that it is not part of the p-nitrophenol degradation pathway. Key enzymes involved in degradation of methyl parathion and in conversion of p-nitrophenol to 4-nitrocatechol, namely parathion hydrolase and p-nitrophenol hydroxylase component "A" were detected in the proteomes of the methyl parathion and p-nitrophenol grown cultures, respectively. These studies report for the first time the existence of a p-nitrophenol hydroxylase component "A", typically found in Gram-positive bacteria, in a Gram-negative strain of the genus Serratia.

Abstract  Methyl parathion is a widely used agricultural insecticide, and the recent unlicensed use of this compound in homes has led to the evacuation of approximately 1100 persons in Mississippi. Although the primary concern in such cases of acute exposure is neurotoxicity, a few organophosphorus compounds apparently have immunotoxic effects at dosages that do not produce neurotoxic symptoms. The purpose of the present study was to determine if this is the case for methyl parathion. Female B6C3F1 mice were exposed to methyl parathion by gavage, daily for 7, 14, 2 1, or 28 d (at 6 mg/kg/d). Exposure for 14-28 d produced significant, dose-responsive inhibition of acetylcholin-esterase (the target molecule for methyl parathion-induced neurotoxicity) in brain or plasma, indicating that the compound was active. The following immunological parameters were evaluated: white blood cell counts and differentials, spleen and thymus weight and cellularity, splenic natural killer cell activity, nitrite production by peritoneal macrophages following activation in vitro, antibody response to sheep erythrocytes in vitro and in vivo, the cytotoxic T lymphocyte response to allogeneic tumor cells, and resistance to Streptococcus agalactiae and B16F10 melanoma cells. Methylparathion at 1 or 3 mg/kg/d significantly increased splenic natural killer cell activity. Nitrite production by macrophages was increased in mice treated with 1, 3, or 6 mg/kg/d. The antibody response to sheep erythrocytes in vitro was significantly suppressed, but the humoral response to sheep erythrocytes in vivo was not affected. The cytotoxic T-lymphocyte response to allogeneic tumor cells was not significantly affected. Host resistance was not significantly decreased. Although it remains possible that immunological parameters not tested here may be affected by methyl parathion, the present results do not suggest substantial immunotoxic potential for this compound.

Abstract  Past disposal of wastewaters containing 2,4,6-trinitrotoluene (TNT) at the former Nebraska Ordnance Plant has resulted in numerous acres of TNT-contaminated soil. Examining the microbial population of these soils revealed several TNT-tolerant Pseudomonas spp. We selected one species, P. savastanoi, to determine its ability to transform TNT. Pure culture experiments were performed in pseudomonas minimal medium containing 0.31 mM TNT (70 mg TNT . L(-1)) under varied nutrient and cell density regimes. Experiments with TNT as a sole C or N source showed that P. savastanoi has the ability to denitrate TNT, as evidenced by production of 2,4-dinitrotoluene (2,4-DNT) and NO2- with time. TNT denitration and formation of 2,4-DNT were enhanced by removing NH4+ and adding NO2- to the growth medium. In all experiments, 2-amino-4,6-dinitrotoluene (2-ADNT) and 4-amino-2,6-dinitrotoluene (4-ADNT) appeared as incidental reduction products. Glucose addition to the medium enhanced 2-ADNT and 4-ADNT production and decreased denitration of TNT. Mid-log phase cells rapidly transformed [ring-14C(U)]TNT but were unable to mineralize significant quantities of TNT, as evidenced by conversion of less than 1% of the label to 14CO2. These results indicate that P. savastanoi is a TNT-tolerant pseudomonad that can promote TNT degradation through reductive denitration and nitro moiety reduction.

Abstract  The long-term changes of acidifying deposition in Finland during the period 1973-2000 were studied using bulk deposition data from 19 stations belonging to the national monitoring network. The regional-scale approach (southern, central and northern Finland) was used for trend assessment with respect to implementation of European sulphur (S) emission reduction amendments involving deposition changes prior to (1973-1985) and after (1986-2000) the agreements (S protocols in 1985 and 1994). There were no marked changes in sulphate deposition between the 1970s and 1980s and consistent trends in 1973-1985 were not observed. Deposition of nitrogen (N) compounds, particularly NO3-N, were increasing between the 1970s and 1980s. Deposition of base cations exhibited a slight decline throughout the 1970s and 1980s. Decrease of calcium and magnesium deposition without corresponding decrease in sulphate resulted in increased acidifying potential (AP) of deposition. Due to successful implementation of S (and N) emission reduction measures, sulphate deposition has decreased substantially (30% in northern and up to 60% in southern Finland) since the late 1980s. N deposition also decreased, but less than S deposition. Base cation deposition has also declined substantially, but this decline appeared to be leveling off during the 1990s, accounting for the decrease of AP in deposition. The observed deposition pattern is in agreement with the on-going biochemical recovery of acidified small Finnish lakes taking place since the early 1990s. (C) 2003 Elsevier Ltd. All rights reserved.

Abstract  Knowledge of the spatially resolved composition of atmospheric particles is essential for differentiating between their surface versus bulk chemistry and understanding particle reactivity and the potential environmental impact. We demonstrate the application of nanometer-scale secondary ion mass spectrometry (CAMECA NanoSIMS 50 ion probe) for 3D chemical imaging of individual atmospheric particles without any sample pre-treatment, such as sectioning of particles. Use of NanoSIMS depth profile analysis enables elemental mapping of particles with nanometer spatial resolution over a broad range of particle sizes. We have used this technique to probe the spatially resolved composition of ambient particles collected during a field campaign in Mexico City. Particles collected during this campaign have been extensively characterized in the past using other particle analysis techniques and hence offer a unique opportunity for exploring the utility of depth-resolved chemical imaging in ambient particle research. Particles examined in this study include those collected during a pollution episode related to urban waste incineration as well as background particles from the same location before the episode. Particles from the pollution episode show substantial intra-particle compositional variability typical of particles resulting from multiple emission sources. In contrast, the background particles have relatively homogeneous compositions with enhanced presence of nitrogen, oxygen, and chlorine at the particle surface. The observed surface enhancement of nitrogen and oxygen species is consistent with the presence of surface nitrates resulting from gas-particle heterogeneous interactions and is indicative of atmospheric ageing of the particles. The results presented here illustrate 3D characterization of ambient particles for insight into their chemical history.

Abstract  Human activity has substantially increased atmospheric NO3- deposition in many regions of the Earth, which could lead to the N saturation of terrestrial ecosystems. Sugar maple (Acer saccharum Marsh.) dominated northern hardwood forests in the Upper Great Lakes region may be particularly sensitive to chronic NO3- deposition, because relatively moderate experimental increases (three times ambient) have resulted in substantial N leaching over a relatively short duration (5-7 years). Although microbial immobilization is an initial sink (i.e., within 1-2 days) for anthropogenic NO3- in this ecosystem, we have an incomplete understanding of the processes controlling the longer-term (i.e., after 1 year) retention and flow of anthropogenic N. Our objectives were to determine: (i) whether chronic NO3- additions have altered the N content of major ecosystem pools, and (ii) the longer-term fate of (NO3-)-N-15 in plots receiving chronic NO3- addition. We addressed these objectives using a field experiment in which three northern hardwood plots receive ambient atmospheric N deposition (ca. 0.9 g N m(-2) year(-1)) and three plots which receive ambient plus experimental N deposition (3.0 g NO3--N m(-2) year(-1)). Chronic NO3- deposition significantly increased the N concentration and content (g N/m(2)) of canopy leaves, which contained 72% more N than the control treatment. However, chronic NO3- deposition did not significantly alter the biomass, N concentration or N content of any other ecosystem pool. The largest portion of 15 N recovered after 1 year occurred in overstory leaves and branches (10%). In contrast, we recovered virtually none of the isotope in soil organic matter (SOM), indicating that SOM was not a sink for anthropogenic NO3- over a 1 year duration. Our results indicate that anthropogenic NO3- initially assimilated by the microbial community is released into soil solution where it is subsequently taken up by overstory trees and allocated to the canopy. Anthropogenic N appears to be incorporated into SOM only after it is returned to the forest floor and soil via leaf litter fall. Short- and long-term isotope tracing studies provided very different results and illustrate the need to understand the physiological processes controlling the flow of anthropogenic N in terrestrial ecosystems and the specific time steps over which they operate.

Abstract  The red spruce (Picea rubens Sarg.) - Fraser fir (Abies fraseri (Pursh) Poir.) forest of the southern Appalachians contains a significant amount of coarse woody debris (CWD) that may affect the nitrogen (N) export signal in streams originating from this N-saturated system. Interpretation of the N sink versus source status of CWD of red spruce and Fraser fir was dependent on the method used. Over a chronosequence of decay, (1) N concentrations suggested a N sink (i.e., a net gain of N of 923% in red spruce and 563% in Fraser fir relative to N in live trees); (2) N contents that reflected changes in density suggested a smaller N sink (i.e., a net gain of N of 218% in red spruce and 125% in Fraser fir relative to N in live trees), but the stoichiometry of N and C suggested a N source in early stages of decay and a N source in the most advanced stage of decay only; and (3) N contents that reflected changes in volume suggested a N source (i.e., a net N loss of -172% in red spruce and -122% in Fraser fir). The C/N ratios in CWD suggested that the shift from a N source to a N sink represented a shift from the mobilization of dissolved organic N to the immobilization of ammonium N and (or) nitrate N. The magnitude of the net change in N contents in both red spruce and Fraser fir was amongst the highest reported in literature, suggesting that CWD plays a particularly important role in N dynamics in N saturated forests.

Abstract  The growth of forest species in soil development chronosequences becomes increasingly phosphorus (P)-limited with time, as P is weathered, eroded and leached from soil. Foliar nitrogen (N) concentrations also tend to decrease with soil age when vegetation may be limited in both N and P. Here we report on soil development in temperate rain forests along three New Zealand chronosequences that have minimal pollution and disturbance from human activities, at Franz Josef, Waitutu and Central Volcanic Plateau, and on factors influencing soil net N mineralization (aerobic; 56 days) and foliar N and P concentrations. Except in very young soils (< 500 years), at least 85% of total-P in mineral soil (0-10 cm) was transformed to organic-P. In each chronosequence, total-P declined with time, and foliar N:P ratios (mass) generally increased from 8 to 15-18, suggesting P was more limiting than N in the oldest soils of the chronosequence. There was a negative relationship between net N mineralization and C:N ratio for mineral soil. For the FH (organic) layer, net N mineralization had the strongest relationships with total-N concentration (positively) and C:organic-P ratio (negatively); however, relationships varied with forest group, suggesting that other factors were also important. Foliar P of kamahi (Weinmannia racemosa Linn. f.), a dominant canopy species, was related to soil organic-P, suggesting mineralization was an important process for tree nutrition.Foliar N was positively related to N concentration in the FH layer, but was not significantly related to any measured property in mineral soil, possibly because of the wide range of soils. The consistent declines in both soil and foliar P across the contrasting chronosequences strongly suggest that vegetation becomes progressively P-limited during long-term ecosystem development.

Abstract  A modified filter technique to separate particles and gaseous HNO3 is described, which is based on the use of filters of the Millipore FPLG type in combination with a virtual impactor. It enables routine measurements of gaseous HNO3 in the atmosphere at background levels. Some results of measurements both in the marine background and over rural and semi-rural continental regions are presented.