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  • 1
    ISSN: 1573-515X
    Keywords: Bouteloua eriopoda ; Chihuahuan Desert ; desertification ; hydrology ; Larrea tridentata ; nitrogen ; nutrient budgets ; phosphorus ; runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Losses of dissolved nutrients (N, P, K, Ca, Mg, Na,Cl, and SO4) in runoff were measured on grasslandand shrubland plots in the Chihuahuan desert ofsouthern New Mexico. Runoff began at a lowerthreshold of rainfall in shrublands than ingrasslands, and the runoff coefficient averaged 18.6%in shrubland plots over a 7-year period. In contrast,grassland plots lost 5.0 to 6.3% of incidentprecipitation in runoff during a 5.5-year period. Nutrient losses from shrubland plots were greater thanfrom grassland plots, with nitrogen losses averaging0.33 kg ha−1 yr−1 vs0.15 kg ha−1 yr−1, respectively, during a 3-year period. Thegreater nutrient losses in shrublands were due tohigher runoff, rather than higher nutrientconcentrations in runoff. In spite of these nutrientlosses in runoff, all plots showed net accumulationsof most elements due to inputs from atmosphericdeposition. Therefore, loss of soil nutrients byhillslope runoff cannot, by itself, account for thedepletion of soil fertility associated withdesertification in the Chihuahuan desert.
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  • 2
    ISSN: 1573-515X
    Keywords: gaseous ; kinetics ; mercury ; methods ; speciation ; waters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Mercury evasion from water is commonly modeled using measurements of dissolved gaseous mercury (DGM). We developed a method using a recently available automated field-ready mercury vapor analyzer to rapidly measure the concentrations of DGM in surface waters. We summarize here results of laboratory tests of the method, field intercomparisons with a manual method, and selected data from recent sampling campaigns in Florida and Michigan. The method uses the 1.5 lpm flow of a Tekran® Model 2537A mercury analyzer to purge and analyze discrete water samples, generating near real time (5-min) data on DGM in samples and blanks. Application of the Tekran allowed for detailed analysis of DGM removal kinetics and short-term diel studies characterizing the influence of sunlight and precipitation on DGM production in surface waters. Gas removal kinetics for dozens of samples indicates a first-order rate constant, and supports a 20-min. purge time for surface water samples from Florida (40-min for Michigan samples). Blanks are measured during a second such purge. Our results indicate that DGMs determined by both automated and manual methods are generally comparable, and that DGM in Florida samples is unstable during storage (loss rate constant ∼0.1--0.2 h-1), probably due to oxidation. This suggests that rapid in-field analysis is preferred to storage with delayed analysis. Our data indicate that DGM at the Florida site is influenced by inputs of reactive Hg in rainwater, and by production of surface DGM during photoreduction of oxidized Hg in the water column.
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  • 3
    ISSN: 1573-515X
    Keywords: C:N ratio ; dissolved organic carbon ; dissolved organic nitrogen ; nitrogen ; stream chemistry ; watershed
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Relatively high deposition ofnitrogen (N) in the northeastern United States hascaused concern because sites could become N saturated.In the past, mass-balance studies have been used tomonitor the N status of sites and to investigate theimpact of increased N deposition. Typically, theseefforts have focused on dissolved inorganic forms ofN (DIN = NH4-N + NO3-N) and have largelyignored dissolved organic nitrogen (DON) due todifficulties in its analysis. Recent advances in themeasurement of total dissolved nitrogen (TDN) havefacilitated measurement of DON as the residual of TDN− DIN. We calculated DON and DIN budgets using data onprecipitation and streamwater chemistry collected from9 forested watersheds at 4 sites in New England. TDNin precipitation was composed primarily of DIN. Netretention of TDN ranged from 62 to 89% (4.7 to 10 kghaminus 1 yrminus 1) of annual inputs. DON made up themajority of TDN in stream exports, suggesting thatinclusion of DON is critical to assessing N dynamicseven in areas with large anthropogenic inputs of DIN.Despite the dominance of DON in streamwater,precipitation inputs of DON were approximately equalto outputs. DON concentrations in streamwater did notappear significantly influenced by seasonal biologicalcontrols, but did increase with discharge on somewatersheds. Streamwater NO3-N was the onlyfraction of N that exhibited a seasonal pattern, withconcentrations increasing during the winter months andpeaking during snowmelt runoff. Concentrations ofNO3-N varied considerably among watersheds andare related to DOC:DON ratios in streamwater. AnnualDIN exports were negatively correlated withstreamwater DOC:DON ratios, indicating that theseratios might be a useful index of N status of uplandforests.
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  • 4
    ISSN: 1573-515X
    Keywords: acid deposition ; atmospheric deposition ; nitrate ; nitrification ; nitrogen ; soil carbon ; soil chemistry ; stream water acidification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Cumulative effects of atmospheric N deposition mayincrease N export from watersheds and contribute tothe acidification of surface waters, but naturalfactors (such as forest productivity and soildrainage) that affect forest N cycling can alsocontrol watershed N export. To identify factors thatare related to stream-water export of N, elevationalgradients in atmospheric deposition and naturalprocesses were evaluated in a steep, first-orderwatershed in the Catskill Mountains of New York, from1991 to 1994. Atmospheric deposition of SO 4 2− , andprobably N, increased with increasing elevation withinthis watershed. Stream-water concentrations ofSO 4 2− increased with increasing elevationthroughout the year, whereas stream-waterconcentrations of NO 3 − decreased withincreasing elevation during the winter and springsnowmelt period, and showed no relation with elevationduring the growing season or the fall. Annual exportof N in stream water for the overall watershed equaled12% to 17% of the total atmospheric input on thebasis of two methods of estimation. This percentagedecreased with increasing elevation, from about 25%in the lowest subwatershed to 7% in the highestsubwatershed; a probable result of an upslope increasein the thickness of the surface organic horizon,attributable to an elevational gradient in temperaturethat slows decomposition rates at upper elevations. Balsam fir stands, more prevalent at upper elevationsthan lower elevations, may also affect the gradient ofsubwatershed N export by altering nitrification ratesin the soil. Variations in climate and vegetationmust be considered to determine how future trends inatmospheric deposition will effect watershed export ofnitrogen.
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  • 5
    ISSN: 1573-515X
    Keywords: carbon ; landscape geochemical flows ; model ; nitrogen ; phosphorus ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The importance of landscape geochemical flows wasinvestigated using a dynamic model simulating carbon,nitrogen and phosphorus cycling in riverine wetlands,which has been described in a previous paper. Thehydro-geomorphic unit (HGMU) concept was incorporatedin the model by defining a separate, completeunit-model for each unit (HGMU) within the wetland.These unit-models were connected by defining the flowsof nitrogen and phosphorus between them. These flows,also called landscape geochemical flows, usuallyconsist of flows of water containing N and P. The model was applied to a site at Kismeldon Meadows,in south-western England. This site consists of twounits, a slope and a floodplain, separated by a ditch,which catches most of the run off and shallowgroundwater flows from the slope. Only an estimated1% of the N and P that leaves the slope unit in thewater outflow reaches the floodplain unit; the rest iscaught in the system of ditches, which prevent thegeochemical flows taking their natural course. Toexamine the influence of this system of ditches, themodel was run for the same site, but without theditches. This is comparable to a situation of arestored site, where run off and shallow groundwaterflows containing nutrients, can freely get from theslope to the floodplain. The computer simulation experiment reconnecting theslope and floodplain showed that this (1) increasedthe nutrient input into the floodplain, causing ahigher biomass production, and (2) increased thewetness of the floodplain, causing slowerdecomposition, which together (3) led to a faster soilorganic matter accumulation in the floodplain.Nutrient inflows became relatively more importantcompared to atmospheric deposition, especially forphosphorus. By connecting the slope and the floodplainmore nitrogen and less phosphorus flowed into theriver.
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  • 6
    ISSN: 1573-515X
    Keywords: chloride ; internal eutrophication ; nitrogen ; peat soil ; phosphorus ; phytometer ; sulphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Inputs of surface waters high in chloride and sulphateincreased the availability of nutrients in fenpeatlands. This `internal eutrophication' wasdemonstrated with test plants (`phytometers') andthrough water and soil analysis. Three experiments arepresented in which the level of chloride and/orsulphate was increased to 3 mmolc l−1. Inexperiment 1 chloride levels were increased from 0.5to 3 mmolc l−1 as CaCl2 or NaCl. Inexperiment 2 and 3 similar increased levels forchloride and sulphate (3 mmolc l−1; as NaCland Na2SO4) were used. The following resultswere found: (i) No differences in soil total-N and total-P werefound before and after the treatments in any of thethree experiments. (ii) Experiment 1 showed a significant increase inBio-Available P (BAP) in pots planted with Anthoxanthum odoratum as well as in bare pots for theNaCl and CaCl2 treatments. The plants in thesetreatments had taken up much more P. (iii) Experiment 2 showed an increase in soil BAPafter treatment with chloride and sulphate in potsplanted with Anthoxanthum odoratum. The chloridetreatment had no effect on plant biomass, whereas thesulphate treatment resulted in a reduction in rootbiomass and root N and P content. The shoots showedan increase in P content in the sulphate and chloridetreatments, while N content remained the same. (iv) In experiment 3, treatments with chloride andsulphate led to significantly increased biomass and Puptake of Anthoxanthum odoratum. Again, noeffects on N uptake were found. These experiments provide evidence for distinctlyincreased availability of phosphate in peat soils whenthese come into contact with water with evenmoderately increased sulphate or chloride levels.Surface water originating from the Rhine river, whichis enriched in chloride and sulphate, is oftensupplied to fen reserves in The Netherlands, tocompensate for water losses due to agriculturaldrainage in the region. The results of this study showthat phosphate availability to the vegetation may risedrastically, with detrimental effects on the speciesdensity and the occurrence of rare species in thevegetation. Hence, supply of this water should beavoided.
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  • 7
    ISSN: 1573-868X
    Keywords: Osaka Bay ; sediment ; carbon ; nitrogen ; organic matter ; stable isotope ratio ; terrestrial organic matter ; TOC ; POC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract Carbon and nitrogen stable isotope ratios (δ13C and δ15N) of surface sediments were measured within Osaka Bay, in the Seto Inland Sea in Japan, in order to better understand the sedimentation processes operating on both terrestrial and marine organic matter in the Bay. The δ13C and δ15N of surface sediments in the estuary of the Yodo River were less than −23‰ and 5‰ respectively, but increased in the area up to about 10 km from the river mouth. At greater distances they became constant (giving δ13C of about −20‰ and δ15N about 6‰). It can be concluded that large amounts of terrestrial organic matter exist near the mouth of the Yodo River. Stable isotope ratios in the estuary of the Yodo River within 10 km of the river mouth were useful indicators allowing study of the movement of terrestrial organic matter. Deposition rates for total organic carbon (TOC) and total nitrogen (TN) over the whole of the Bay were estimated to be 63,100 ton C/year and 7,590 ton N/year, respectively. The deposition rate of terrestrial organic carbon was estimated to be 13,200 (range 2,000–21,500) ton C/year for the whole of Osaka Bay, and terrestrial organic carbon was estimated to be about 21% (range 3–34) of the TOC deposition rate. The ratio of the deposition rate of terrestrial organic carbon to the rate inflow of riverine TOC and particulate organic carbon (POC) were estimated to be 19% (range 3–31) and 76% (range 12–100), respectively.
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  • 8
    ISSN: 1573-515X
    Keywords: Baltic Sea ; cyanobacteria ; estuaries ; grazing ; iron ; lakes ; molybdenum ; nitrogen ; nitrogen fixation ; nitrogen limitation ; Zooplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Explaining the nearly ubiquitous absence of nitrogen fixation by planktonic organisms in strongly nitrogen-limited estuaries presents a major challenge to aquatic ecologists. In freshwater lakes of moderate productivity, nitrogen limitation is seldom maintained for long since heterocystic, nitrogen-fixing cyanobacteria bloom, fix nitrogen, and alleviate the nitrogen limitation. In marked contrast to lakes, this behavior occurs in only a few estuaries worldwide. Primary production is limited by nitrogen in most temperate estuaries, yet no measurable planktonic nitrogen fixation occurs. In this paper, we present the hypothesis that the absence of planktonic nitrogen fixers from most estuaries is due to an interaction of bottom-up and top-down controls. The availability of Mo, a trace metal required for nitrogen fixation, is lower in estuaries than in freshwater lakes. This is not an absolute physiological constraint against the occurrence of nitrogen-fixing organisms, but the lower Mo availability may slow the growth rate of these organisms. The slower growth rate makes nitrogen-fixing cyanobacteria in estuaries more sensitive to mortality from grazing by Zooplankton and benthic organisms. We use a simple, mechanistically based simulation model to explore this hypothesis. The model correctly predicts the timing of the formation of heterocystic, cyanobacterial blooms in freshwater lakes and the magnitude of the rate of nitrogen fixation. The model also correctly predicts that high Zooplankton biomasses in freshwaters can partially suppress blooms of nitrogen-fixing cyanobacteria, even in strongly nitrogen-limited lakes. Further, the model indicates that a relatively small and environmentally realistic decrease in Mo availability, such as that which may occur in seawater compared to freshwaters due to sulfate inhibition of Mo assimilation, can suppress blooms of heterocystic cyanobacteria and prevent planktonic nitrogen fixation. For example, the model predicts that at a Zooplankton biomass of 0.2 mg l−1, cyanobacteria will bloom and fix nitrogen in lakes but not in estuaries of full-strength seawater salinity because of the lower Mo availability. Thus, the model provides strong support for our hypothesis that bottom-up and top-down controls may interact to cause the absence of planktonic nitrogen fixation in most estuaries. The model also provides a basis for further exploration of this hypothesis in individual estuarine systems and correctly predicts that planktonic nitrogen fixation can occur in low salinity estuaries, such as the Baltic Sea, where Mo availability is greater than in higher salinity estuaries.
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  • 9
    ISSN: 1573-515X
    Keywords: N15 ; nitrogen ; nutrient cycling ; plants ; stable isotopes ; soil ; temperate forest ; tropical forest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Several lines of evidence suggest that nitrogen in most tropical forests is relatively more available than N in most temperate forests, and even that it may function as an excess nutrient in many tropical forests. If this is correct, tropical forests should have more open N cycles than temperate forests, with both inputs and outputs of N large relative to N cycling within systems. Consequent differences in both the magnitude and the pathways of N loss imply that tropical forests should in general be more 15N enriched than are most temperate forests. In order to test this hypothesis, we compared the nitrogen stable isotopic composition of tree leaves and soils from a variety of tropical and temperate forests. Foliar δ15N values from tropical forests averaged 6.5‰ higher than from temperate forests. Within the tropics, ecosystems with relatively low N availability (montane forests, forests on sandy soils) were significantly more depleted in 15N than other tropical forests. The average δ15N values for tropical forest soils, either for surface or for depth samples, were almost 8‰ higher than temperate forest soils. These results provide another line of evidence that N is relatively abundant in many tropical forest ecosystems.
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  • 10
    ISSN: 1573-515X
    Keywords: estuaries ; lakes ; marine ; nitrogen ; phosphorus ; rivers ; streams ; temperate ; tropics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Published data and analyses from temperate and tropical aquatic systems are used to summarize knowledge about the potential impact of land-use alteration on the nitrogen biogeochemistry of tropical aquatic ecosystems, identify important patterns and recommend key needs for research. The tropical N-cycle is traced from pre-disturbance conditions through the phases of disturbance, highlighting major differences between tropical and temperate systems that might influence development strategies in the tropics. Analyses suggest that tropical freshwaters are more frequently N-limited than temperate zones, while tropical marine systems may show more frequent P limitation. These analyses indicate that disturbances to pristine tropical lands will lead to greatly increased primary production in freshwaters and large changes in tropical freshwater communities. Increased freshwater nutrient flux will also lead to an expansion of the high production, N- and light-limited zones around river deltas, a switch from P- to N-limitation in calcareous marine systems, with large changes in the community composition of fragile mangrove and reef systems. Key information gaps are highlighted, including data on mechanisms of nutrient transport and atmospheric deposition in the tropics, nutrient and material retention capacities of tropical impoundments, and N/P coupling and stoichiometric impacts of nutrient supplies on tropical aquatic communities. The current base of biogeochemical data suggests that alterations in the N-cycle will have greater impacts on tropical aquatic ecosystems than those already observed in the temperate zone.
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  • 11
    ISSN: 1573-515X
    Keywords: Baltic Sea ; cyanobacteria ; estuaries ; grazing ; iron ; lakes ; molybdenum ; nitrogen ; nitrogen fixation ; nitrogen limitation ; zooplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Explaining the nearly ubiquitous absence of nitrogen fixation by planktonic organisms in strongly nitrogen-limited estuaries presents a major challenge to aquatic ecologists. In freshwater lakes of moderate productivity, nitrogen limitation is seldom maintained for long since heterocystic, nitrogen-fixing cyanobacteria bloom, fix nitrogen, and alleviate the nitrogen limitation. In marked contrast to lakes, this behavior occurs in only a few estuaries worldwide. Primary production is limited by nitrogen in most temperate estuaries, yet no measurable planktonic nitrogen fixation occurs. In this paper, we present the hypothesis that the absence of planktonic nitrogen fixers from most estuaries is due to an interaction of bottom-up and top-down controls. The availability of Mo, a trace metal required for nitrogen fixation, is lower in estuaries than in freshwater lakes. This is not an absolute physiological constraint against the occurrence of nitrogen-fixing organisms, but the lower Mo availability may slow the growth rate of these organisms. The slower growth rate makes nitrogen-fixing cyanobacteria in estuaries more sensitive to mortality from grazing by zooplankton and benthic organisms. We use a simple, mechanistically based simulation model to explore this hypothesis. The model correctly predicts the timing of the formation of heterocystic, cyanobacterial blooms in freshwater lakes and the magnitude of the rate of nitrogen fixation. The model also correctly predicts that high zooplankton biomasses in freshwaters can partially suppress blooms of nitrogen-fixing cyanobacteria, even in strongly nitrogen-limited lakes. Further, the model indicates that a relatively small and environmentally realistic decrease in Mo availability, such as that which may occur in seawater compared to freshwaters due to sulfate inhibition of Mo assimilation, can suppress blooms of heterocystic cyanobacteria and prevent planktonic nitrogen fixation. For example, the model predicts that at a zooplankton biomass of 0.2 mg l−1, cyanobacteria will bloom and fix nitrogen in lakes but not in estuaries of full-strength seawater salinity because of the lower Mo availability. Thus, the model provides strong support for our hypothesis that bottom-up and top-down controls may interact to cause the absence of planktonic nitrogen fixation in most estuaries. The model also provides a basis for further exploration of this hypothesis in individual estuarine systems and correctly predicts that planktonic nitrogen fixation can occur in low salinity estuaries, such as the Baltic Sea, where Mo availability is greater than in higher salinity estuaries.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Biogeochemistry 44 (1999), S. 93-118 
    ISSN: 1573-515X
    Keywords: Everglades National Park ; mangrove soils ; organic matter ; nitrogen ; phosphorus ; sedimentation ; simulation model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The distribution and accumulation of organic matter, nitrogen (N) and phosphorus (P) in mangrove soils at four sites along the Shark River estuary of south Florida were investigated with empirical measures and a process-based model. The mangrove nutrient model (NUMAN) was developed from the SEMIDEC marsh organic matter model and parameterized with data from mangrove wetlands. The soil characteristics in the four mangrove sites varied greatly in both concentrations and profiles of soil carbon, N and P. Organic matter decreased from 82% in the upstream locations to 30% in the marine sites. Comparisons of simulated and observed results demonstrated that landscape gradients of soil characteristics along the estuary can be adequately modeled by accounting for plant production, litter decomposition and export, and allochthonous input of mineral sediments. Model sensitivity analyses suggest that root production has a more significant effect on soil composition than litter fall. Model simulations showed that the greatest change in organic matter, N, and P occurred from the soil surface to 5 cm depth. The rapid decomposition of labile organic matter was responsible for this decrease in organic matter. Simulated N mineralization rates decreased quickly with depth, which corresponded with the decrease of labile organic matter. The increase in organic matter content and decrease in soil bulk density from mangrove sites at downstream locations compared to those at upstream locations was controlled mainly by variation in allochthonous inputs of mineral matter at the mouth of the estuary, along with gradients in mangrove root production. Research on allochthonouns sediment input and in situ root production of mangroves is limited compared to their significance to understanding nutrient biogeochemistry of these wetlands. More accurate simulations of temporal patterns of nutrient characteristics with depth will depend on including the effects of disturbance such as hurricanes on sediment redistribution and biomass production.
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  • 13
    ISSN: 1573-515X
    Keywords: Chaohu Lake ; chemical fertilizer ; cycling ; denitrification ; multipond system ; nitrogen ; nutrient budget ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract During a two-year field study, an annual nutrient budget and cycles were developed for a small agricultural watershed. The study emphasized the integrated unit of the watershed in understanding the biogeochemistry. It was found that the total nutrient input was 39.1× 104 kg nitrogen and 3.91×104 kg phosphorus in the year 1995, of which the greatest input of nutrients to the watershed was chemical fertilizer application, reaching 34.7×104 kg (676 kg/ha) nitrogen and 3.88×104 kg (76 kg/ha) phosphorus. The total nutrient output from the watershed was 13.55×104 kg nitrogen and 0.40×104 kg phosphorus, while the largest output of nitrogen was denitrification, accounting for 44.1% of N output; the largest output of phosphorus was sale of crops, accounting for 99.4% of P output. The results show that the nutrient input is larger than output, demonstrating that there is nutrient surplus within the watershed, a surplus which may become a potential source of nonpoint pollution to area waters. The research showed that both denitrification and volatilization of nitrogen are key ways of nitrogen loss from the watershed. This suggests that careful management of fertilizer application will be important for the sustainable development of agriculture. The research demonstrated that a multipond system within the watershed had high retention rate for both water and nutrients, benefiting the water, nutrient and sediment recycling in the terrestrial ecosystem and helping to reduce agricultural nonpoint pollution at its source. Therefore, this unique watershed system should be recommended due to its great potential relevance for sustainable agricultural development.
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  • 14
    ISSN: 1573-515X
    Keywords: Chihuahuan desert ; desert ; desertification ; grassland ; nitrogen ; nutrient budgets ; phosphorus ; runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rainfall simulation experiments were performed in areas of semiarid grassland (Bouteloua eriopoda) and arid shrubland (Larrea tridentata) in the Chihuahuan desert of New Mexico. The objective was to compare the runoff of nitrogen (N) and phosphorus (P) from these habitats to assess whether losses of soil nutrients are associated with the invasion of grasslands by shrubs. Runoff losses from grass- and shrub-dominated plots were similar, and much less than from bare plots located in the shrubland. Weighted average concentrations of total dissolved N compounds in runoff were greatest in the grassland (1.72 mg/1) and lowest in bare plots in the shrubland (0.55 mg/1). More than half of the N transported in runoff was carried in dissolved organic compounds. In grassland and shrub plots, the total N loss was highly correlated to the total volume of discharge. We estimate that the total annual loss of N in runoff is 0.25 kg/ha/yr in grasslands and 0.43 kg/ha/yr in shrublands — consistent with the depletion of soil N during desertification of these habitats. Losses of P from both habitats were very small.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Biogeochemistry 44 (1999), S. 93-118 
    ISSN: 1573-515X
    Keywords: Everglades National Park ; mangrove soils ; organic matter ; nitrogen ; phosphorus ; sedimentation ; simulation model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The distribution and accumulation of organic matter, nitrogen (N) and phosphorus (P) in mangrove soils at four sites along the Shark River estuary of south Florida were investigated with empirical measures and a process-based model. The mangrove nutrient model (NUMAN) was developed from the SEMIDEC marsh organic matter model and parameterized with data from mangrove wetlands. The soil characteristics in the four mangrove sites varied greatly in both concentrations and profiles of soil carbon, N and P. Organic matter decreased from 82% in the upstream locations to 30% in the marine sites. Comparisons of simulated and observed results demonstrated that landscape gradients of soil characteristics along the estuary can be adequately modeled by accounting for plant production, litter decomposition and export, and allochthonous input of mineral sediments. Model sensitivity analyses suggest that root production has a more significant effect on soil composition than litter fall. Model simulations showed that the greatest change in organic matter, N, and P occurred from the soil surface to 5 cm depth. The rapid decomposition of labile organic matter was responsible for this decrease in organic matter. Simulated N mineralization rates decreased quickly with depth, which corresponded with the decrease of labile organic matter. The increase in organic matter content and decrease in soil bulk density from mangrove sites at downstream locations compared to those at upstream locations was controlled mainly by variation in allochthonous inputs of mineral matter at the mouth of the estuary, along with gradients in mangrove root production. Research on allochthonouns sediment input and in situ root production of mangroves is limited compared to their significance to understanding nutrient biogeochemistry of these wetlands. More accurate simulations of temporal patterns of nutrient characteristics with depth will depend on including the effects of disturbance such as hurricanes on sediment redistribution and biomass production.
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  • 16
    ISSN: 1573-515X
    Keywords: Chaohu Lake ; chemical fertilizer ; cycling ; denitrification ; multipond system ; nitrogen ; nutrient budget ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract During a two-year field study, an annual nutrient budget and cycles were developed for a small agricultural watershed. The study emphasized the integrated unit of the watershed in understanding the biogeochemistry. It was found that the total nutrient input was 39.1 × 104 kg nitrogen and 3.91 × 104 kg phosphorus in the year 1995, of which the greatest input of nutrients to the watershed was chemical fertilizer application, reaching 34.7 × 104 kg (676 kg/ha) nitrogen and 3.88 × 104 kg (76 kg/ha) phosphorus. The total nutrient output from the watershed was 13.55 × 104 kg nitrogen and 0.40 × 104 kg phosphorus, while the largest output of nitrogen was denitrification, accounting for 44.1% of N output; the largest output of phosphorus was sale of crops, accounting for 99.4% of P output. The results show that the nutrient input is larger than output, demonstrating that there is nutrient surplus within the watershed, a surplus which may become a potential source of nonpoint pollution to area waters. The research showed that both denitrification and volatilization of nitrogen are key ways of nitrogen loss from the watershed. This suggests that careful management of fertilizer application will be important for the sustainable development of agriculture. The research demonstrated that a multipond system within the watershed had high retention rate for both water and nutrients, benefiting the water, nutrient and sediment recycling in the terrestrial ecosystem and helping to reduce agricultural nonpoint pollution at its source. Therefore, this unique watershed system should be recommended due to its great potential relevance for sustainable agricultural development.
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  • 17
    ISSN: 1573-515X
    Keywords: atmospheric deposition ; moss ; bog ; nitrogen ; phosphorus ; water table
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen additions as NH4NO3 corresponding to 0 (N0), 1 (N1), 3 (N3) and 10 (N10) g N m−2 yr−1 were made toSphagnum magellanicurn cores at two-week intervalsin situ at four sites across Europe, i.e. Lakkasuo (Finland). Männikjärve (Estonia), Moidach More (UK) and Côte de Braveix (France). The same treatments were applied in a glasshouse experiment in Neuchâtel (Switzerland) in which the water table depth was artificially maintained at 7, 17 and 37 cm below the moss surface. In the field, N assimilation in excess of values in wet deposition occurred in the absence of growth, but varied widely between sites, being absent in Lakkasuo (moss N∶P ratio 68) and greatest in Moidach More (N∶P 21). In the glasshouse, growth was reduced by lowering the water table without any apparent effect on N assimilation. Total N content of the moss in field sites increased as the mean depth of water table increased indicating growth limitation leading to increased N concentrations which could reduce the capacity for N retention. Greater contents of NH4 + in the underlying peat at 30 cm depth, both in response to NH4NO3 addition and in the unamended cores confirmed poor retention of inorganic N by the moss at Lakkasuo. Nitrate contents in the profiles at Lakkasuo, Moidach More, and Côte de Braveix were extremely low, even in the N10 treatment, but in Männikjärve, where the mean depth of water table was greatest and retention absent, appreciable amounts of NO3 − were detected in all cores. It is concluded that peatland drainage would reduce the capture of inorganic N in atmospheric deposition bySphagnum mosses.
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  • 18
    ISSN: 1573-515X
    Keywords: N15 ; nitrogen ; nutrient cycling ; plants ; stable isotopes ; soil ; temperate forest ; tropical forest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Several lines of evidence suggest that nitrogen in most tropical forests is relatively more available than N in most temperate forests, and even that it may function as an excess nutrient in many tropical forests. If this is correct, tropical forests should have more open N cycles than temperate forests, with both inputs and outputs of N large relative to N cycling within systems. Consequent differences in both the magnitude and the pathways of N loss imply that tropical forests should in general be more15N enriched than are most temperate forests. In order to test this hypothesis, we compared the nitrogen stable isotopic composition of tree leaves and soils from a variety of tropical and temperate forests. Foliar δ15N values from tropical forests averaged 6.5‰ higher than from temperate forests. Within the tropics, ecosystems with relatively low N availability (montane forests, forests on sandy soils) were significantly more depleted in15N than other tropical forests. The average δ15N values for tropical forest soils, either for surface or for depth samples, were almost 8‰ higher than temperate forest soils. These results provide another line of evidence that N is relatively abundant in many tropical forest ecosystems.
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  • 19
    ISSN: 1573-515X
    Keywords: estuaries ; lakes ; marine ; nitrogen ; phosphorus ; rivers ; streams ; temperate ; tropics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Published data and analyses from temperate and tropical aquatic systems are used to summarize knowledge about the potential impact of land-use alteration on the nitrogen biogeochemistry of tropical aquatic ecosystems, identify important patterns and recommend key needs for research. The tropical N-cycle is traced from pre-disturbance conditions through the phases of disturbance, highlighting major differences between tropical and temperate systems that might influence development strategies in the tropics. Analyses suggest that tropical freshwaters are more frequently N-limited than temperate zones, while tropical marine systems may show more frequent P limitation. These analyses indicate that disturbances to pristine tropical lands will lead to greatly increased primary production in freshwaters and large changes in tropical freshwater communities. Increased freshwater nutrient flux will also lead to an expansion of the high production, N- and light-limited zones around river deltas, a switch from P- to N-limitation in calcareous marine systems, with large changes in the community composition of fragile mangrove and reef systems. Key information gaps are highlighted, including data on mechanisms of nutrient transport and atmospheric deposition in the tropics, nutrient and material retention capacities of tropical impoundments, and N/P coupling and stoichiometric impacts of nutrient supplies on tropical aquatic communities. The current base of biogeochemical data suggests that alterations in the N-cycle will have greater impacts on tropical aquatic ecosystems than those already observed in the temperate zone.
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  • 20
    ISSN: 1573-515X
    Keywords: acetate ; carbon dioxide ; hydrogen ; methanogenesis ; iron ; organic carbon ; nitrogen ; redox balance ; rice paddy soil ; sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The potentials for sequential reduction of inorganic electron acceptors and production of methane have been examined in sixteen rice soils obtained from China, the Philippines, and Italy. Methane, CO2, Fe(II), NO 3 - , SO 4 2 , pH, Eh, H2 and acetate were monitored during anaerobic incubation at 30 °C for 120 days. Based on the accumulation patterns of CO2 and CH4, the reduction process was divided into three distinct phases: (1) an initial reduction phase during which most of the inorganic electron acceptors were depleted and CO2 production was at its maximum, (2) a methanogenic phase during which CH4 production was initiated and reached its highest rate, and (3) a steady state phase with constant production rates of CH4 and CO2. The reduction phases lasted for 19 to 75 days with maximum CO2 production of 2.3 to 10.9 μmol d-1 g-1 dry soil. Methane production started after 2 to 87 days and became constant after about 38--68 days (one soil 〉120 days). The maximum CH4 production rates ranged between 0.01 and 3.08 μmol d-1 g-1. During steady state the constant CH4 and CO2 production rates varied from 0.07 to 0.30 μmol d-1 g-1 and 0.02 and 0.28 μmol d-1 g-1, respectively. Within the 120 d of anaerobic incubation only 6--17% of the total soil organic carbon was released into the gas phase. The gaseous carbon released consisted of 61--100% CO2, 〈0.1--35% CH4, and 〈5% nonmethane hydrocarbons. Associated with the reduction of available Fe(III) most of the CO2 was produced during the reduction phase. The electron transfer was balanced between total CO2 produced and both CH4 formed and Fe(III), sulfate and nitrate reduced. Maximum CH4 production rate (r = 0.891) and total CH4 produced (r = 0.775) correlated best with the ratio of soil nitrogen to electron acceptors. Total nitrogen content was a better indicator for “available” organic substrates than the total organic carbon content. The redox potential was not a good predictor of potential CH4 production. These observations indicate that the availability of degradable organic substrates mainly controls the CH4 production in the absence of inorganic electron acceptors.
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  • 21
    ISSN: 1573-515X
    Keywords: acetate ; carbon dioxide ; hydrogen ; methanogenesis ; iron ; organic carbon ; nitrogen ; redox balance ; rice paddy soil ; sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The potentials for sequential reduction of inorganic electron acceptors and production of methane have been examined in sixteen rice soils obtained from China, the Philippines, and Italy. Methane, CO2, Fe(II), NO 3 − , SO 4 2− , pH, Eh, H2 and acetate were monitored during anaerobic incubation at 30 °C for 120 days. Based on the accumulation patterns of CO2 and CH4, the reduction process was divided into three distinct phases: (1) an initial reduction phase during which most of the inorganic electron acceptors were depleted and CO2 production was at its maximum, (2) a methanogenic phase during which CH4 production was initiated and reached its highest rate, and (3) a steady state phase with constant production rates of CH4. and CO2. The reduction phases lasted for 19 to 75 days with maximum CO2 production of 2.3 to 10.9μmol d−1 g−1 dry soil. Methane production started after 2 to 87 days and became constant after about 38–68 days (one soil 〉120 days). The maximum CH4 production rates ranged between 0.01 and 3.08μmol d−1 g−1. During steady state the constant CH4 and CO2 production rates varied from 0.07 to 0.30μmol d−1 g−1 and 0.02 and 0.28μmol d−1 g−1, respectively. Within the 120 d of anaerobic incubation only 6–17% of the total soil organic carbon was released into the gas phase. The gaseous carbon released consisted of 61–100% CO2, 〈0.1–35% CH4, and 〈5% nonmethane hydrocarbons. Associated with the reduction of available Fe(III) most of the CO2 was produced during the reduction phase. The electron transfer was balanced between total CO2 produced and both CH4 formed and Fe(III), sulfate and nitrate reduced. Maximum CH4 production rate (r=0.891) and total CH4 produced (r =0.775) correlated best with the ratio of soil nitrogen to electron acceptors. Total nitrogen content was a better indicator for “available” organic substrates than the total organic carbon content. The redox potential was not a good predictor of potential CH4 production. These observations indicate that the availability of degradable organic substrates mainly controls the CH4 production in the absence of inorganic electron acceptors.
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  • 22
    ISSN: 1573-0662
    Keywords: atmosphere ; kinetics ; nitrate radical ; monoterpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, α-phellandrene, d-limonene, terpinolene and γ-terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, α-phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and γ-terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and α-phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[−(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[−(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and γ-terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.
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  • 23
    ISSN: 1573-0662
    Keywords: δ3-carene ; chlorine atoms ; isoprene ; kinetics ; methacrolein and methyl vinyl ketone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.
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  • 24
    ISSN: 1573-515X
    Keywords: atmospheric deposition ; moss ; bog ; nitrogen ; phosphorus ; water table
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen additions as NH4NO3 corresponding to 0 (N0), 1 (N1), 3 (N3) and 10 (N10) g N m-2 yr-1 were made to Sphagnum magellanicum cores at two-week intervals in situ at four sites across Europe, i.e. Lakkasuo (Finland), Männikjärve (Estonia), Moidach More (UK) and Côte de Braveix (France). The same treatments were applied in a glasshouse experiment in Neuchâtel (Switzerland) in which the water table depth was artificially maintained at 7, 17 and 37 cm below the moss surface. In the field, N assimilation in excess of values in wet deposition occurred in the absence of growth, but varied widely between sites, being absent in Lakkasuo (moss N:P ratio 68) and greatest in Moidach More (N:P 21). In the glasshouse, growth was reduced by lowering the water table without any apparent effect on N assimilation. Total N content of the moss in field sites increased as the mean depth of water table increased indicating growth limitation leading to increased N concentrations which could reduce the capacity for N retention. Greater contents of NH4+ in the underlying peat at 30 cm depth, both in response to NH4NO3 addition and in the unamended cores confirmed poor retention of inorganic N by the moss at Lakkasuo. Nitrate contents in the profiles at Lakkasuo, Moidach More, and Côte de Braveix were extremely low, even in the N10 treatment, but in Männikjärve, where the mean depth of water table was greatest and retention absent, appreciable amounts of NO3- were detected in all cores. It is concluded that peatland drainage would reduce the capture of inorganic N in atmospheric deposition by Sphagnum mosses.
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  • 25
    ISSN: 1573-515X
    Keywords: Chihuahuan desert ; desert ; desertification ; grassland ; nitrogen ; nutrient budgets ; phosphorus ; runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rainfall simulation experiments were performed in areas of semiarid grassland (Bouteloua eriopoda) and arid shrubland (Larrea tridentata) in the Chihuahuan desert of New Mexico. The objective was to compare the runoff of nitrogen (N) and phosphorus (P) from these habitats to assess whether losses of soil nutrients are associated with the invasion of grasslands by shrubs. Runoff losses from grass- and shrub-dominated plots were similar, and much less than from bare plots located in the shrubland. Weighted average concentrations of total dissolved N compounds in runoff were greatest in the grassland (1.72 mg/l) and lowest in bare plots in the shrubland (0.55 mg/l). More than half of the N transported in runoff was carried in dissolved organic compounds. In grassland and shrub plots, the total N loss was highly correlated to the total volume of discharge. We estimate that the total annual loss of N in runoff is 0.25 kg/ha/yr in grasslands and 0.43 kg/ha/yr in shrublands – consistent with the depletion of soil N during desertification of these habitats. Losses of P from both habitats were very small.
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  • 26
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    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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  • 27
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    Biology and fertility of soils 26 (1998), S. 169-172 
    ISSN: 1432-0789
    Keywords: Key words Urea ; Coated fertilizers ; Ammonium ; nitrogen ; Nitrate nitrogen ; Nitrogen uptake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Understanding the fate of different forms of nitrogen (N) fertilizers applied to soils is an important step in enhancing N use efficiency and minimizing N losses. The growth and N uptake of two citrus rootstocks, Swingle citrumelo (SC), and Cleopatra mandarin (CM), seedlings were evaluated in a pot experiment using a Candler fine sand (hyperthermic, uncoated, Typic Quartzipsamments) without N application or with 400 mg N kg–1 applied as urea or controlled-release fertilizers (CRF; either as Meister, Osmocote, or Poly-S). Meister and Osmocote are polyolefin resin-coated urea with longevity of N release for 270 days (at 25°C). Poly-S is a polymer and sulfur-coated urea with release duration considerably shorter than that of either Meister or Osmocote. The concentrations of 2 M KCl extractable nitrate nitrogen (NO3 –-N) and ammonium nitrogen (NH4 +-N) in the soil sampled 180 days and 300 days after planting were greater in the soil with SC than with CM rootstock seedlings. In most cases, the extractable NH4 + and NO3 – concentrations were greater for the Osmocote treatment compared to the other N sources. For the SC rootstock seedlings, dry weight was greater with Meister or Poly-S compared with either Osmocote or urea. At the end of the experiment, ranking of the various N sources, with respect to total N uptake by the seedlings, was: Meister = Osmocote 〉 Poly-S 〉 Urea 〉 no N for CM rootstock, and Meister = Poly-S = Osmocote 〉 Urea 〉 no N for SC rootstock. The study demonstrated that for a given rate of N application the total N uptake by seedlings was greater for the CRF compared to urea treatment. This suggests that various N losses were lower from the CRF source as compared to those from soluble fertilizers.
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  • 28
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    Biogeochemistry 43 (1998), S. 63-78 
    ISSN: 1573-515X
    Keywords: carbon ; mass balance ; nitrogen ; nitrogen fixation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Ecosystems with high rates of nitrogen fixation often have high loss rates through leaching or possibly denitrification. However, there is no formal theoretical context to examine why this should be the case nor of how nitrogen accumulates in such open systems. Here, we propose a simple model coupling nitrogen inputs and losses to carbon inputs and losses. The nitrogen balance of this model system depends on plant (nitrogen fixer) growth rate, its carrying capacity, N fixed/C fixed, residence time of nitrogen and carbon in biomass, litter decay rate, litter N/C, and fractional loss rate of mineralized nitrogen. The model predicts the requirements for equilibrium in a nitrogen-fixing system, and the conditions on nitrogen fixation and losses in order for the system to accumulate nitrogen and carbon. In particular, the accumulation of nitrogen and carbon in a nitrogen-fixing system depend on an interaction between residence time in vegetation and litter decay rate in soil. To reflect a possible increased uptake of soil nitrogen and decreased respiratory cost of symbiotic nitrogen fixers, the model was then modified so that fixation rate decreased and growth rate increased as nitrogen capital accumulated. These modifications had only small effects on carbon and nitrogen accumulation. This suggests that switching from uptake of atmospheric nitrogen to mineral soil nitrogen as nitrogen capital accumulates simply results in a trade-off between energetic limitations and soil nitrogen limitations to carbon and nitrogen accumulation. Experimental tests of the model are suggested.
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  • 29
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    Biogeochemistry 42 (1998), S. 169-187 
    ISSN: 1573-515X
    Keywords: aridisols ; desertification ; erosion ; geostatistics ; Larrea tridentata ; nitrogen ; phosphorus ; Prosopis glandulosa ; soil heterogeneity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Geostatistical analyses show that the distribution of soil N, P and K is strongly associated with the presence of shrubs in desert habitats. Shrubs concentrate the biogeochemical cycle of these elements in ‘islands of fertility’ that are localized beneath their canopies, while adjacent barren, intershrub spaces are comparatively devoid of biotic activity. Both physical and biological processes are involved in the formation of shrub islands. Losses of semiarid grassland in favor of invading shrubs initiate these changes in the distribution of soil nutrients, which may promote the further invasion and persistence of shrubs and cause potential feedbacks between desertification and the Earth's climate system.
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  • 30
    ISSN: 1573-0662
    Keywords: peroxy radicals ; kinetics ; conjugateddienes ; biogenic VOC ; degradation mechanisms ; tropospheric ozone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The laser flash photolysis/UV absorption spectrometry technique has been used to investigate the kinetics of the peroxy radical permutation reactions (i.e. self and cross reactions) arising from the OH-initiated oxidation of isoprene (2-methyl-1,3-butadiene), and of the simpler, but related conjugated dienes, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene. The results of the two simpler systems are analysed to provide values of the rate coefficients for the 6 peroxy radical permutation reactions of the three types of isomeric peroxy radical produced in each system (T = 298 K, P = 760 Torr). The rate coefficients are all significantly larger than values estimated previously by extrapolation of structure-reactivity relationships based on the kinetics of a limited dataset of simpler radicals containing similar structural features. The results are discussed in terms of trends in self and cross reaction reactivity of primary, secondary and tertiary peroxy radicals containing combinations of allyl, β-hydroxy and δ-hydroxy functionalities. Since the peroxy radicals formed in these systems are structurally very similar to those formed in the isoprene system, the kinetic parameters derived from the results of the simpler systems are used to assist the assignment of kinetic parameters to the 21 permutation reactions of the six types of isomeric peroxy radical generated in the isoprene system. Kinetic models describing the OH-initiated degradation of all three conjugated dienes to first generation products in the absence of NOx are recommended, which are also consistent with available end product studies. The model for isoprene is considered to be a further improvement on that suggested previously for its OH-initiated oxidation in the absence of NOx. The mechanism is further extended to include chemistry applicable to ‘NOx-present’ conditions, and calculated product yields are compared with those reported in the literature.
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  • 31
    ISSN: 1573-0662
    Keywords: hydroxyl radical ; nitrate radical ; ozone ; pinonaldehyde ; caronaldehyde ; sabinaketone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10−12 cm3 molecule−1 s−1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10−14 cm3 molecule−1 s−1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of 〈2 × 10−20 cm3 molecule−1 s−1 for pinonaldehyde and caronaldehyde, and 〈5 × 10−20 cm3 molecule−1 s−1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.
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  • 32
    ISSN: 1432-0789
    Keywords: Key words Microbial biomass C ; Water-soluble organic carbon ; Light fraction organic carbon ; Fertilizer ; nitrogen ; 13C nuclear magnetic resonance ; Infrared spectrophotometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Soil samples taken from four experimental sites that had been cropped to continuous corn for 3–11 years in Ontario and Quebec were analyzed to evaluate changes in quantity and quality of labile soil organic carbon under different nitrogen (N) fertility and tillage treatments. Addition of fertilizer N above soil test recommendations tended to decrease amounts of water-soluble organic carbon (WSOC) and microbial biomass carbon (MBC). The quality of the WSOC was characterized by 13C nuclear magnetic resonance and infrared spectrophotometry and the results indicated that carbohydrates, long-chain aliphatics and proteins were the major components of all extracts. Similar types of C were present in all of the soils, but an influence of management was evident. The quantity of soil MBC was positively related to the quantities of WSOC, carbohydrate C, and organic C, and negatively related to quantities of long-chain aliphatic C in the soil. The quantity of WSOC was positively related to the quantities of protein C, carbohydrate C, and negatively related to the quantity of carboxylic C. The quantity of soil MBC was not only related to quantities of soil WSOC but also to the quality of soil WSOC.
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  • 33
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    Biology and fertility of soils 26 (1997), S. 31-34 
    ISSN: 1432-0789
    Keywords: Key words Microbial biomass ; Air-drying ; Extractable ; nitrogen ; Extractable phosphorus ; Tropical soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The microbial contribution to extractable N and P after the air-drying of eight Indian dry tropical Ultisols was quantified. Air-drying of the soils decreased microbial biomass C by 25–53% but increased extractable N and P by 14–34% and 24–121%, respectively. This increase in the extractable N and P was accounted for, to some extent, by microbial biomass killed due to air-drying. Microbial biomass contributes 17–36% and 19–82% to the extractable N and P, respectively, possibly due to air-drying of the soils. I conclude that due to contamination of microbial biomass with the available nutrients in air-dried soils, measurements of extractable nutrients should be made on field-moist soils.
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  • 34
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    Biogeochemistry 36 (1997), S. 189-203 
    ISSN: 1573-515X
    Keywords: ammonia volatilization ; grassland ; nitrogen ; ungulate ; Yellowstone National Park
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured ammonia volatilization at three topographic positions(hilltop, mid-slope, slope-bottom) on three grassland landscapes at threetimes during 1995 (April, May, July) on the northern winter range ofYellowstone National Park that supports large herds of native ungulates.Percent ammonia-N lost from all sites during the study ranged 1–24%of urea-N applied. Volatilization among sites was negatively related tosoil cation-exchange capacity (r = –0.85) and rates were highest inJuly. We used the relationship between soil CEC and percent Nvolatilized from urea-amended plots to estimate annual ammonia-Nvolatilization from 5 sites for which annual ungulate urine inputs werepreviously determined (Frank et al. 1994). Estimated mean annualammonia-N volatilized from those sites was 1.4 kg/ha/yr, which wasless than a previously reported regional atmospheric deposition rate (2kg/ha/yr; Swank 1984). Results indicate the need to understand theinteraction between (1) spatially heterogeneous patterns of soilprocesses, and 2) nonuniform patterns of ungulate use of landscapes todetermine rates of ecosystem-level N-gaseous loss. Findings alsosuggest that ammonia-N volatilized from urine patches should not leadto a decline in soil N in this ecosystem.
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  • 35
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    Biogeochemistry 37 (1997), S. 237-252 
    ISSN: 1573-515X
    Keywords: freshwater ; limitation ; marine ; nitrogen ; phosphorus ; ratio ; stoichiometry ; trace elements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen supply is often assumed to limitmarine primary production. A global analysis of totalnitrogen (N) to phosphorus (P) molar ratios shows thattotal N:P is low (〈16:1) in some estuarine andcoastal ecosystems, but up to 100:1 in open oceans.This implies that elements other than N may limitmarine production, except in human impacted, estuarineor coastal ecosystems. This pattern may reconcileconflicting enrichment studies, because N additionfrequently increases phytoplankton growth where totalN:P is expected to be low, but P, Fe, or Si augmentphytoplankton growth in waters where total N:P ishigh. Comparison of total N:P stoichiometry betweenmarine and freshwaters yields a model of the form ofthe aquatic N:P cycle.
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  • 36
    ISSN: 1573-515X
    Keywords: carbon ; nitrogen ; Ohio River ; phosphorus ; Red field ratios ; dissolved organic matter ; rivers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A 12-month study was conducted to measure the concentrations ofdissolved organic matter (DOC, TDN, TDP) in four sites within a119 km long reach of the Ohio River, near Louisville, KY. In thisstudy we test whether specific geomorphological and biologicalfactors influenced variations in dissolved organic matter.Concentrations of DOC in the river averaged ≈1200μmol/L, and varied by nearly two orders of magnitudeseasonally (mean DOC during base flow ≈620 μmol/L).Peak periods for DOC at all sites were during April–May. Thesite nearest a navigation dam (deeper, lower current velocities)had significantly lower concentrations of TDN and greater C:Nratios than upstream sites. The largest tributary entering thisreach (Kentucky River) had no significant effect on levels of DOMin the main river, despite having significantly greaterconcentrations of TDN and lower levels of DOC during most monthsof the year. Concentrations of DOC, TDN, and TDP were notsignificantly different in littoral and pelagic habitats at allsites studied, suggesting little floodplain influence on DOM inthis constricted-channel section of the Ohio River. C:N ratios ofDOM in the Ohio were significantly different among seasons; C:Nexceeded or equaled Redfield ratios in summer and fall (6 to 10),but were below Redfield (1.8 to 3.0) during winter and spring.Regression models suggest that total phytoplankton densities andflow conditions are the two most important factors regulating DOMin this very large river.
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  • 37
    ISSN: 1573-515X
    Keywords: Amazon ; deforestation ; hydrologic pathway ; groundwater ; nitrogen ; rain forest ; slash-and-burn agriculture ; solutes ; tropical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Hydrochemical changes caused by slash-and-burnagricultural practices in a small upland catchment inthe central Amazon were measured. Soluteconcentrations were analyzed in wet deposition,overland flow, shallow throughflow, groundwater andbank seepage in a forested plot (about 5 ha) and anadjacent plot (about 2 ha) which had been deforestedin July 1989 and planted to manioc, and in streamwater in partially deforested and forested catchments. Measurements were made from November 1988 to June1990. The effects of slash-and-burn agriculturalpractices observed in the experimental plot includedincreased overland flow, erosion, and large losses ofsolutes from the rooted zone. Concentrations ofNO3 -, Na+, K+, SO4 2-,Cl- and Mn in throughflow of the experimentalplot were higher than those of the control plot bymore than a factor of 10. Extensive leaching occurredafter cutting and burning, but solute transfers werediminished along pathway stages of throughflow togroundwater, and particularly within the riparian zoneof the catchment. High concentrations of N and P inoverland flow indicate the importance of usingforested riparian buffers to mitigate solute inputs toreceiving waters in tropical catchments.
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  • 38
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    Biogeochemistry 37 (1997), S. 63-75 
    ISSN: 1573-515X
    Keywords: nutrient limitation ; soil development ; nitrogen ; phosphorus ; chronosequence ; Hawai'i
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Walker & Syers (1976) proposed a conceptual model that describesthe pattern and regulation of soil nutrient pools and availability during long-term soil and ecosystem development. Their model implies that plantproduction generally should be limited by N on young soils and by P on oldsoils; N and P supply should more or less equilibrate onintermediate-aged soils. We tested the application of this model to nutrientlimitation, using a well characterized substrate age sequence in Hawaiianmontane rain forest. Earlier experiments had evaluated nutrient limitationin forests on a young (300 y) and an old (4,100,000 y) substrate on the samedevelopmental sequence; N alone limited tree growth on the youngsubstrate, while P alone did so on the old one. An additional fertilizerexperiment based on replicated treatments with N, P, and all othernutrients combined, applied in individually and in all factorialcombinations, was established in an intermediate-aged site in theLaupahoehoe Forest Reserve, Hawaii. Here, diameter increments of thedominant tree Metrosideros polymorpha increased slightly with Nadditions, and nearly doubled when N and P were added together.Additions of elements other than N and P had no significant effecton growth. These results show that N and P had equilibrated (relativeto plant requirements) in the intermediate aged site. Together withthe earlier experiments, these results suggest that the Walker and Syersmodel provides a useful starting point for explaining the nature anddistribution of nutrient limitation in forest ecosystems.
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  • 39
    ISSN: 1573-515X
    Keywords: aluminium ; forest soils ; lysimeters ; nitrification ; nitrogen ; roots
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The effects of enhanced (NH4 2SO4deposition on soil solution cation and anion concentrations and annualionic fluxes were followed using a standardised experimental protocolin six European coniferous forests with contrasting soil types, pollutioninputs and climate. Native soil cores containing a ceramic suction cupwere installed in the field, roofed and watered every two weeks withlocal throughfall or local throughfall with added(NH4)2SO4 at 75 kgNH4 +-N ha-1 a-1. Livingroot systems were established in half of the lysimeters.Untreated throughfall NH4 +-N deposition at thesites ranged from 3.7 to 29 kg ha-1 a-1Soil leachates were collected at two weekly intervalsover 12 months and analysed for volume, andconcentrations of major anions and cations. Increasesin soil solution NO3 - concentrations inresponse to N additions were observed after 4–9months at three sites, whilst one sandy soil with highC:N ratio failed to nitrify under any of thetreatments. Changes in NO3 - concentrationsin soil solution controlled soil solution cationconcentrations in the five nitrifying soils, withAl3+ being the dominant cation in the more acidsoils with low base saturation. The acidification responses ofthe soils to the (NH4 2SO4additions were primarily related to the ability of thesoils to nitrify the added NH4 +. pH and soiltexture seemed important in controllingNH4 + leaching in response to the treatments,with two less acidic, clay/clay loam sites showingalmost total retention of added NH4 +, whilstnearly 75% of the added N was leached asNH4 + at the acid sandy soils. The presenceof living roots significantly reduced soil solutionNO3 - and associated cation concentrations attwo of the six sites. The very different responses of the sixsoils to increased (NH4)2SO4deposition emphasise that the establishment of N critical loadsfor forest soils need to allow for differences in N storagecapacity and nitrification potential.
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  • 40
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    Biogeochemistry 39 (1997), S. 1-13 
    ISSN: 1573-515X
    Keywords: 226Ra accumulation ; background level ; natural zones ; terrestrial animals ; nitrogen ; rain forest ; slash-and-burn agriculture ; solutes ; tropical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Radium (226Ra) accumulation by terrestrial animalswas studied in the territory of the former USSR. Concentrations of226Ra in different soils, plants and animals aresimilar to the background level. For soils it fluctuates in range0.5–1.5 × 10-12 gg-1 (18.3–55 Bq/kg), for plantsbetween 0.1–1.7 × 10-12 gg-1 (3.7–62.1 Bq/kg), and for animals– 0.02–1.5 ×10-12 g g-1(0.73–55 Bq/kg). There were no significant differences in226Ra concentration between animals of different groups. Themaximal 226Ra concentration is marked for the woodlouse Hemilepistus aphganicus from the Badkhyz reserve in Turkmenistan– 1.49 × 10-12g g-1 of dwt (54.4 Bq/kg), the minimal one– for Colorado beetle Leptinotarsadecemlineata from the vicinity of Moscow – 0.02× 10-12 gg-1 of dwt (0.73 Bq/kg). Concentration ratios for linkssoil – plant, plant – animal andprey – carnivore are usually close to 1. A hypothesison the similarity of 226Raconcentration in different animals is discussed.
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  • 41
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    Pure and applied geophysics 147 (1996), S. 367-375 
    ISSN: 1420-9136
    Keywords: Induced seismicity ; kinetics ; rock fracture ; rockburst ; earthquake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Powerful seismic events, such as earthquakes and rockbursts, are caused by the accumulation of energy in rocks and loss of rock mass stability. Usually methods of their forecasting are based on the registration of anomalous behavior of geophysical fields. However an efficiency of this approach is low. The present paper proposes a kinetic approach to the description of rock fracture process, which can be used for the forecasting of seismic events and an investigation of structure and energy distributions in rock. 3-D and 1-D kinetic equations describing a process of cluster formation in rock were obtained. The equations are invariant to deformation conditions and to the scale level of events. They showed a good agreement with the results of field observations and laboratory experiments. It was also shown that these equations well describe the processes of earthquake, rockburst and rock sample failure preparation. Catalogues of rockbursts in mines were analyzed with the use of the kinetic equations to find out evidence of induced seismic events. The proposed approach makes it possible to reveal trends in rock behavior and thus predict the rock failure at different scale levels.
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  • 42
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    Biogeochemistry 32 (1996), S. 93-113 
    ISSN: 1573-515X
    Keywords: alpine ; biogeochemistry ; nitrogen ; nitrogen saturation ; snowmelt ; soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Experiments were conducted during 1993 at Niwot Ridge in the Colorado Front Range to determine if the insulating effect of winter snow cover allows soil microbial activity to significantly affect nitrogen inputs and outputs in alpine systems. Soil surface temperatures under seasonal snowpacks warmed from −14 °C in January to 0 °C by May 4th. Snowmelt began in mid-May and the sites were snow free by mid June. Heterotrophic microbial activity in snow-covered soils, measured as C02 production, was first identified on March 4, 1993. Net C02 flux increased from 55 mg CO2-C m−2 day−1 in early March to greater than 824 mg CO2-C m-2 day−1 by the middle of May. Carbon dioxide production decreased in late May as soils became saturated during snowmelt. Soil inorganic N concentrations increased before snowmelt, peaking between 101 and 276 mg kg−1 soil in May, and then decreasing as soils became saturated with melt water. Net N mineralization for the period of March 3 to May 4 ranged from 2.23 to 6.63 g N m−2, and were approximately two orders of magnitude greater than snowmelt inputs of 50.4 mg N m−2 for NH4 + and 97.2 mg N m−2 for NO3 −. Both NO3 − and NH4 + concentrations remained at or below detection limits in surface water during snowmelt, indicating the only export of inorganic N from the system was through gaseous losses. Nitrous oxide production under snow was first observed in early April. Production increased as soils warned, peaking at 75 μg N2O-N m−2 day−1 in soils saturated with melt water one week before the sites were snow free. These data suggest that microbial activity in snow-covered soils may play a key role in alpine N cycling before plants become active.
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  • 43
    ISSN: 1573-515X
    Keywords: lacustrine sediment ; organic matter ; sedimentation rates ; recycling ; burial ; carbon ; nitrogen ; silicon ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The areal distribution of organic C contents, δ13C values, total N and P and biogenic Si contents in surficial sediments were used to study the distribution, origin and diagenetic transformations of sedimented biogenic debris in the eutrophic subalpine Lake Bled (Slovenia), which for most of the yearhas an anoxic hypolimnion. The influence of an allochthonous input, restricted to the western basin, was clearly traced by higher organic C and total N and P contents, higher δ13C values, and higher sedimentation rate in comparison to the eastern basin. The low δ13C values of sedimentary organic matter in the major part of the lake, lower than the δ13C values of different types of organic matter, suggest that this sedimentary organic matter is most probably the product of a microbial community and not a residue of primary production. The temporal variation of benthic diffusive fluxes of NH4, Si and PO4, derived from modelling the pore water profiles, was related to sedimentation of phytoplanktonic blooms, while the PO4 fluxes were also dependent on changing redox conditions at the sediment-water interface in the period of the winter-spring overtum. The removal of PO4 in pore waters is probably due to the adsorption of phosphate and precipitation of apatite and vivianite. The budget of C, N and P at the sediment-water interface revealed a high recycling efficiency (〉70%), also confirmed by the rather uniform (or only slightly decreasing) vertical profiles of organic C, total N and P in sediment cores and C/N and C/P ratios. The percentage of biogenic Si recycling is low (〈10%), suggesting its removal in sediments.
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  • 44
    ISSN: 1573-515X
    Keywords: continental shelf ; estuaries ; mass balance ; nitrogen ; North Atlantic ; nutrient budget ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Five large rivers that discharge on the western North Atlantic continental shelf carry about 45% of the nitrogen (N) and 70% of the phosphorus (P) that others estimate to be the total flux of these elements from the entire North Atlantic watershed, including North, Central and South America, Europe, and Northwest Africa. We estimate that 61 · 109 moles y−1 of N and 20 · 109 moles y−1 of P from the large rivers are buried with sediments in their deltas, and that an equal amount of N and P from the large rivers is lost to the shelf through burial of river sediments that are deposited directly on the continental slope. The effective transport of active N and P from land to the shelf through the very large rivers is thus reduced to 292 · 109 moles y−1 of N and 13 · 109 moles y−1 of P. The remaining riverine fluxes from land must pass through estuaries. An analysis of annual total N and total P budgets for various estuaries around the North Atlantic revealed that the net fractional transport of these nutrients through estuaries to the continental shelf is inversely correlated with the log mean residence time of water in the system. This is consistent with numerous observations of nutrient retention and loss in temperate lakes. Denitrification is the major process responsible for removing N in most estuaries, and the fraction of total N input that is denitrified appears to be directly proportional to the log mean water residence time. In general, we estimate that estuarine processes retain and remove 30–65% of the total N and 10–55% of the total P that would otherwise pass into the coastal ocean. The resulting transport through estuaries to the shelf amounts to 172–335 · 109 moles y−1 of N and 11–19 · 109 moles y−1 of P. These values are similar to the effective contribution from the large rivers that discharge directly on the shelf. For the North Atlantic shelf as a whole, N fluxes from major rivers and estuaries exceed atmospheric deposition by a factor of 3.5–4.7, but this varies widely among regions of the shelf. For example, on the U.S. Atlantic shelf and on the northwest European shelf, atmospheric deposition of N may exceed estuarine exports. Denitrification in shelf sediments exceeds the combined N input from land and atmosphere by a factor of 1.4–2.2. This deficit must be met by a flux of N from the deeper ocean. Burial of organic matter fixed on the shelf removes only a small fraction of the total N and P input (2–12% of N from land and atmosphere; 1–17% of P), but it may be a significant loss for P in the North Sea and some other regions. The removal of N and P in fisheries landings is very small. The gross exchange of N and P between the shelf and the open ocean is much larger than inputs from land and, for the North Atlantic shelf as a whole, it may be much larger than the N and P removed through denitrification, burial, and fisheries. Overall, the North Atlantic continental shelf appears to remove some 700–950· 109 moles of N each year from the deep ocean and to transport somewhere between 18 and 30 · 109 moles of P to the open sea. If the N and P associated with riverine sediments deposited on the continental slope are included in the total balance, the net flux of N to the shelf is reduced by 60 · 109 moles y−1 and the P flux to the ocean is increased by 20 · 109 moles y−1. These conclusions are quite tentative, however, because of large uncertainties in our estimates of some important terms in the shelf mass balance.
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  • 45
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    Journal of atmospheric chemistry 24 (1996), S. 23-37 
    ISSN: 1573-0662
    Keywords: hydroxyl radical ; dimethylsulfoxide ; kinetics ; sulfur cycle
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10-10 cm3 molecule-1 s-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10-17 cm2, where the large uncertainty results from experimental difficulties associated with the low vapor pressure and ‘stickiness’ of DMSO.
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  • 46
    ISSN: 1573-515X
    Keywords: fertilizer study ; Hawaii ; montane tropical forest ; nitrogen ; phosphorus ; primary succession
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We applied fertilizers in a 23complete factorial design to determine the effects of nutrient amendments on plant growth in Hawaiian montane forests growing on two different volcanic substrates: ‘a‘ā and pāhoehoe lava. Both sites were about 140 years old and their overstories were nearly monospecific stands of Metrosideros polymorpha. Fertilizer applications included N, P, a mixture of essential macro- and micronutrients excepting P and N, and all combinations thereof in each of four blocks. Additions of nutrients other than N or P had no significant effects on measured plant-growth variables. In contrast, additions of either N or P significantly increased tree height growth, diameter increments, biomass growth, and height growth of the understory fern Dicranopteris linearis in both sites. The effect of N was greater than that of P. Greatest growth rates occurred in plots receiving both N and P, and signficant N*P interactions occurred in several cases, suggesting a synergistic effect between these two elements. Plant growth on these young, poorly weathered, basaltic lavas is colimited by N and P availability. Growth in a similar-aged stand growing on a mixture of volcanic ash and cinders is N but not P limited, indicating that the texture of the parent material influences nutrient-availability patterns during early primary succession.
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  • 47
    ISSN: 1573-515X
    Keywords: biogeochemistry ; mangrove ; sediments ; organic carbon ; nitrogen ; carbonate dissolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The biogeochemistry of mangrove sediments was investigated in several mangrove forest communities in Gazi Bay, a coastal lagoon in Kenya, Africa. Carbon dioxide fluxes, sediment median grain sizes, sedimentary organic carbon, nitrogen and phosphorus contents and pore-water characteristics (ammonium, nitrate, sulfate and chloride) could be related to forest type. Mangrove sediments have pH values that range from 3.5 to 8.3 due to the limited buffer capacity of these sediments and intense acidifying processes such as aerobic degradation of organic matter, oxidation of reduced components, ammonium uptake by roots and root respiration. The mangrove sediments are nitrogen-rich compared to mangrove litter, as a result of microbial nitrogen retention, uptake and fixation, and import of nitrogen-rich material. It appears that mangrove sediments in Gazi Bay act as a nutrient and carbon sink rather than as a source for adjacent seagrass and reef ecosystems.
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  • 48
    ISSN: 1573-515X
    Keywords: anthropogenic ; atmospheric deposition ; eutrophication ; fertilizer ; nitrogen ; nitrogen budget ; nitrogen fixation ; N:P ratio ; phosphorus ; pristine ; rivers ; temperate ; tropical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We present estimates of total nitrogen and total phosphorus fluxes in rivers to the North Atlantic Ocean from 14 regions in North America, South America, Europe, and Africa which collectively comprise the drainage basins to the North Atlantic. The Amazon basin dominates the overall phosphorus flux and has the highest phosphorus flux per area. The total nitrogen flux from the Amazon is also large, contributing 3.3 Tg yr−1 out of a total for the entire North Atlantic region of 13.1 Tg yr−1 . On a per area basis, however, the largest nitrogen fluxes are found in the highly disturbed watersheds around the North Sea, in northwestern Europe, and in the northeastern U.S., all of which have riverine nitrogen fluxes greater than 1,000 kg N km−2 yr−1. Non-point sources of nitrogen dominate riverine fluxes to the coast in all regions. River fluxes of total nitrogen from the temperate regions of the North Atlantic basin are correlated with population density, as has been observed previously for fluxes of nitrate in the world's major rivers. However, more striking is a strong linear correlation between river fluxes of total nitrogen and the sum of anthropogenically-derived nitrogen inputs to the temperate regions (fertilizer application, human-induced increases in atmospheric deposition of oxidized forms of nitrogen, fixation by leguminous crops, and the import/export of nitrogen in agricultural products). On average, regional nitrogen fluxes in rivers are only 25% of these anthropogenically derived nitrogen inputs. Denitrification in wetlands and aquatic ecosystems is probably the dominant sink, with storage in forests perhaps also of importance. Storage of nitrogen in groundwater, although of importance in some localities, is a very small sink for nitrogen inputs in all regions. Agricultural sources of nitrogen dominate inputs in many regions, particularly the Mississippi basin and the North Sea drainages. Deposition of oxidized nitrogen, primarily of industrial origin, is the major control over river nitrogen export in some regions such as the northeastern U.S. Using data from relatively pristine areas as an index of change, we estimate that riverine nitrogen fluxes in many of the temperate regions have increased from pre-industrial times by 2 to 20 fold, although some regions such as northern Canada are relatively unchanged. Fluxes from the most disturbed region, the North Sea drainages, have increased by 6 to 20 fold. Fluxes from the Amazon basin are also at least 2 to 5 fold greater than estimated fluxes from undisturbed temperate-zone regions, despite low population density and low inputs of anthropogenic nitrogen to the region. This suggests that natural riverine nitrogen fluxes in the tropics may be significantly greater than in the temperate zone. However, deforestation may be contributing to the tropical fluxes. In either case, projected increases in fertilizer use and atmospheric deposition in the coming decades are likely to cause dramatic increases in nitrogen loading to many tropical river systems.
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  • 49
    ISSN: 1573-515X
    Keywords: methane oxidation ; methane emission ; soil ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Measurements of the net methane exchange over a range of forest, moorland, and agricultural soils in Scotland were made during the period April to June 1994 and 1995. Fluxes of CH4 ranged from oxidation −12.3 to an emission of 6.8 ng m−2 s−1. The balance between CH4 oxidation and emission depended on the physical conditions of the soil, primarily soil moisture. The largest oxidation rates were found in the mineral forest soils, and CH4 emission was observed in several peat soils. The smallest oxidation rate was observed in an agricultural soil. The relationship between CH4 flux and soil moisture observed in peats (FluxCH 4 = 0.023 × %H2O (dry weight) − 7.44, p 〉 0.05) was such that CH4 oxidation was observed at soil moistures less than 325%( ± 80%). CH4 emission was found at soil moistures exceeding this value. A large range of CH4 oxidation rates were observed over a small soil moisture range in the mineral soils. CH4 oxidation in mineral soils was negatively correlated with soil bulk density (FluxCH 4 = −37.35 × bulk density (g cm−3) + 48.83, p 〉 0.05). Increased nitrogen loading of the soil due to N fixation, atmospheric deposition of N, and fertilisation, were consistently associated with decreases in the soil sink for CH4, typically in the range 50 to 80%, on a range of soil types and land uses.
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  • 50
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    Biogeochemistry 35 (1996), S. 261-274 
    ISSN: 1573-515X
    Keywords: budget ; new production ; nitrogen ; nitrogen fixation ; North Atlantic ; Trichodesmium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The role of nitrogen fixation in the nitrogen cycle of the North Atlantic basin was re-evaluated because recent estimates had indicated a far higher rate than previous reports. Examination of the available data on nitrogen fixation rates and abundance ofTrichodesmium, the major nitrogen fixing organism, leads to the conclusion that rates might be as high as 1.09 × 1012 mol N yr−1. Several geochemical arguments are reviewed that each require a large nitrogen source that is consistent with nitrogen fixation, but the current data, although limited, do not support a sufficiently high rate. However, recent measurements of the fixation rates per colony are higher than the historical average, suggesting that improved methodology may require a re-evaluation through further measurements. The paucity of temporally resolved data on both rates and abundance for the major areal extent of the tropical Atlantic, where aeolian inputs of iron may foster high fixation rates, represents another major gap.
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  • 51
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    Biogeochemistry 35 (1996), S. 235-260 
    ISSN: 1573-515X
    Keywords: benthic mineralization ; continental shelf ; denitrification ; global N cycle ; nitrogen ; North Atlantic ; nutrients ; onwelling ; phytoplankton ; sediments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A model of coupled nitrification/denitrification was developed for continental shelf sediments to estimate the spatial distribution of denitrification throughout shelf regions in the North Atlantic basin. Using data from a wide range of continental shelf regions, we found a linear relationship between denitrification and sediment oxygen uptake. This relationship was applied to specific continental shelf regions by combining it with a second regression relating sediment oxygen uptake to primary production in the overlying water. The combined equation was: denitrification (mmol N m−2 d−1)=0.019* phytoplankton production (mmol C m−2 d−1). This relationship suggests that approximately 13% of the N incorporated into phytoplankton in shelf waters is eventually denitrified in the sediments via coupled nitrification/denitrification, assuming a C:N ratio of 6.625:1 for phytoplankton. The model calculated denitrification rates compare favorably with rates reported for several shelf regions in the North Atlantic. The model-predicted average denitrification rate for continental shelf sediments in the North Atlantic Basin is 0.69 mmol N m− 2 d−1. Denitrification rates (per unit area) predicted by the model are highest for the continental shelf region in the western North Atlantic between Cape Hatteras and South Florida and lowest for Hudson Bay, the Baffin Island region, and Greenland. Within latitudinal belts, average denitrification rates were lowest in the high latitudes, intermediate in the tropics and highest in the mid-latitudes. Although denitrification rates per unit area are lowest in the high latitudes, the total N removal by denitrification (53 × 1010 mol N y−1) is similar to that in the mid-latitudes (60 × 1010 mol N y−1) due to the large area of continental shelf in the high latitudes. The Gulf of St. Lawrence/Grand Banks area and the North Sea are responsible for seventy-five percent of the denitrification in the high latitude region. N removal by denitrification in the western North Atlantic (96 × 1010 mol N y−1) is two times greater than in the eastern North Atlantic (47 × 1010 mol N y−1). This is primarily due to differences in the area of continental shelf in the two regions, as the average denitrification rate per unit area is similar in the western and eastern North Atlantic. We calculate that a total of 143 × 1010 mol N y−1 is removed via coupled nitrification/denitrification on the North Atlantic continental shelf. This estimate is expected to underestimate total sediment denitrification because it does not include direct denitrification of nitrate from the overlying water. The rate of coupled nitrification/denitrification calculated is greater than the nitrogen inputs from atmospheric deposition and river sources combined, and suggests that onwelling of nutrient rich slope water is a major source of N for denitrification in shelf regions. For the two regions where N inputs to a shelf region from onwelling have been measured, onwelling appears to be able to balance the denitrification loss.
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  • 52
    ISSN: 1573-515X
    Keywords: nitrogen ; particulate organic matter ; nutrient cycling ; grassland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A set of long term15N studies was initiated during the summers of 1981 and 1982 on the backslope and footslope, respectively, of a catena in the shortgrass steppe of northeastern Colorado. Microplots labeled with15N urea were sampled for15N and total N content in 1981 and 1982 and again in 1992. In November, 1982, 100% of the added N was recovered in the soil-plant system of the finer-textured footslope, compared to 39% in the coarser-textured backslope microplots. Ten years later,15N recovery of the applied N decreased at both topographic positions to 85% in the footslope and 29% in the backslope. Average losses since the time of application were 3.5 g N m−2yr−1 in the backslope and 0.8 g N m−2yr−1 in the footslope. In 1992, soil organic matter was physically fractionated into particulate (POM) and mineral associated (MAON) fractions and 21-day mineralization incubations were conducted to assess the relative amounts of15N that were in the slow, passive and active soil organic matter pools, respectively, of the two soils. Our findings confirm the assumptions that POM represents a large portion of the slow organic compartment and that the MAON represents a large fraction of the passive compartment defined in the Century model. The N located in the MAON had the lowest availability for plant uptake. Isotopic data were consistent with textural effects and with the Century model compartmentalization of soil organic N based on the residence time of the organic N.
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  • 53
    ISSN: 1573-1421
    Keywords: calcite ; precipitation ; dissolution ; kinetics ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Calcite dissolution rates were measured using a free-drift technique at 25°C, 1 atm total pressure, and various $$P_{CO_2 } $$ in deionized water. The data were corrected for gas phase disequilibrium and fitted to a kinetic expression derived by coupling the mechanistic models of Plummeret al. (1987a) and Chouet al. (1989) to the surface complexation model of Van Cappellenet al. (1993). Corrected dissolution and precipitation rate measurements from previous investigations were combined to our data set and fitted to the same expression. The following reactions provide an adequate description of the calcite dissolution and precipitation mechanism in dilute solutions: for which the overall reaction rate is given by where 〉i are the densities of surface complexes (mol/m2),a i are the activities of dissolved species and,k i are the rate constants corresponding to the above reactions. This rate equation satisfies the principle of microscopic reversibility and applies to both dissolution and precipitation reactions over a wide range of $$P_{CO_2 } $$ , pH and saturation states. The rate constants obtained from fitting the data set to Equation (3) are compatible with values reported by Plummeret al. and Chouet al., as well as yielding a very good estimate of the thermodynamic solubility constant of calcite, K 0 sp .
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  • 54
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    Biogeochemistry 30 (1995), S. 171-189 
    ISSN: 1573-515X
    Keywords: ammonium ; marsh ; mineralization ; nitrate ; nitrification ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Flooding can be an important control of nitrogen (N) biogeochemistry in wetland ecosystems. In North American prairie marshes, spring flooding is a dominant feature of the physical environment that increases emergent plant production and could influence N cycling. I investigated how spring flooding affects N availability and plant N utilization in whitetop (Scolochloa festucacea) marshes in Manitoba, Canada by comparing experimentally spring-flooded marsh inside an impoundment with adjacent nonflooded marsh. The spring-flooded marsh had net N mineralization rates up to 4 times greater than nonflooded marsh. Total growing season net N mineralization was 124 kg N ha−1 in the spring-flooded marsh compared with 62 kg N ha−1 in the nonflooded marsh. Summer water level drawdown in the spring-flooded marsh decreased net N mineralization rates. Net nitrification rates increased in the nonflooded marsh following a lowering of the water table during mid summer. Growing season net nitrification was 33 kg N ha−1 in the nonflooded marsh but 〈 1 kg N ha−1 in the spring-flooded marsh. Added NO3 −1 induced nitrate reductase (NRA) activity in whitetop grown in pot culture. Field-collected plants showed higher NRA in the nonflooded marsh. Nitrate comprised 40% of total plant N uptake in the nonflooded marsh but 〈1% of total N uptake in the spring-flooded marsh. Higher plant N demand caused by higher whitetop production in the spring-flooded marsh approximately balanced greater net N mineralization. A close association between the presence of spring flooding and net N mineralization and net nitrification rates indicated that modifications to prairie marshes that change the pattern of spring inundation will lead to rapid and significant changes in marsh N cycling patterns.
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  • 55
    ISSN: 1573-515X
    Keywords: budget ; carbon ; mass balance ; Narragansett Bay ; nitrogen ; nutrients ; phosphorus
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Narragansett Bay is a relatively well-mixed, high salinity coastal embayment and estuary complex in southern New England (USA). Much of the shoreline is urban and the watershed is densely developed. We have combined our data on C, N, and P inputs to this system, on C, N, and P accumulation in the sediments, and on denitrification with extensive work by others to develop approximate annual mass balances for these elements. The results show that primary production within the bay is the major source of organic carbon (4 times greater than other sources), that land drainage and upstream sewage and fertilizer are the major sources of N, and that landward flowing bottom water from offshore may be a major source of dissolved inorganic phosphorus. Most of the nutrients entering the bay arrive in dissolved inorganic form, though DON is a significant component of the N carried by the rivers. About 40% of the DIN in the rivers is in the form of ammonia. Sedimentation rates are low in most of Narragansett Bay, and it appears that less than 20% of the total annual input of each of these elements is retained within the system. A very small amount of C, N, and P is removed in fisheries landings, denitrification in the sediments removes perhaps 10–25% of the N input, and most of the carbon fixed in the system is respired within it. Stoichiometric calculations suggest that some 10–20% of the organic matter formed in the bay is exported to offshore and that Narragansett Bay is an autotrophic system. Most of the N and P that enters the bay is, however, exported to offshore waters in dissolved inorganic form. This assessment of the overall biogeochemical behavior of C, N, and P in the bay is consistent with more rigorously constrained mass balances obtained using large living models or mesocosms of the bay at the Marine Ecosystem Research Laboratory (MERL).
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  • 56
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    Biogeochemistry 29 (1995), S. 223-235 
    ISSN: 1573-515X
    Keywords: chronosequence ; montane tropical forest ; nitrogen ; nutrient limitation ; phosphorus ; productivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We tested the hypothesis that P was the nutrient limiting net primary production of a nativeMetrosideros polymorpha forest on a highly weathered montane tropical soil in Hawaii. A factorial experiment used all combinations of three fertilizer treatments: nitrogen (N), phosphorus (P) and a mix of other essential nutrients (OE), consisting primarily of mineral derived cations and excluding N and P. P addition, but not N or OE, increased leaf area index within 12 months, foliar P concentration measured at 18 months, and stem diameter increment within 18 months. Stem growth at 18 months was even greater when trees fertilized with P also received the OE treatment. N and P additions increased leaf litterfall and N and P in combination further increased litterfall. The sequence of responses suggests that increased available P promoted an increase in photosynthetic area which led to increased wood production. P was the essential element most limiting to primary production on old volcanic soil in contrast to the N limitation found on young volcanic soils.
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  • 57
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    Aquatic geochemistry 1 (1995), S. 399-426 
    ISSN: 1573-1421
    Keywords: manganese reduction ; manganese oxidation ; organic matter oxidation ; kinetics ; bacteria ; alkalinity ; lake chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The redox processes regulating transport of Mn in the water column of a eutrophic, dimictic lake (Lake Norrviken, Sweden) are interpreted based on a one-dimensional diffusion-reaction model for Mn(II). It is found that rates and rate constants for oxidation and reduction vary greatly with depth and also with time during the season of stratification. Calculated rates show that Mn(II) oxidation and reduction generally occur in narrow depth intervals (25–50 cm). This is in good agreement with measured profiles of particulate Mn (MnO x ). Maximum oxidation rate constants (assuming first order kinetics) at each date are in the first half of the season 〈1 d−1, but then increases to a rather constant value of about 25 d−1. These high rate constants are indicative of microbiological involvement in the Mn(II) oxidation. This is further evidenced by SEM-EDS analysis showing Mn enriched particles morphologically similar toMetallogenium. Reductive dissolution of Mn oxides occurs mainly in the zone just below the zone of maximum oxidation rate. The release of Mn(II) is accompanied by production of alkalinity and ΣCO2. The relation between production rates of Mn(II) and alkalinity indicates that Mn oxides act as terminal electron acceptors in the bacterially mediated oxidation of organic matter. However, the ΔMn2+/ΔΣCO2 ratio is significantly lower than what is expected from this process. It is suggested that the Mn reduction is coupled to fermentation. Close coexistence of Mn reduction and oxidation at high rates, such as found in the water column of this lake, facilitates rapid and continuous regeneration of reducible Mn oxides. This gives rise to a quantitatively important mechanism of organic matter oxidation in the water column.
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  • 58
    ISSN: 1573-0417
    Keywords: Great Basin ; climatic variations ; productivity ; organic matter ; nitrogen ; phosphorus ; hardwater lake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Sediment cores from the shallow and deep basins of Pyramid Lake, Nevada, revealed variations in composition with depth reflecting changes in lake level, river inflow, and lake productivity. Recent sediments from the period of historical record indicate: (1) CaCO3 and organic content of sediment in the shallow basin decrease at lower lake level, (2) CaCO3 content of deep basin sediments increases when lake level decreases rapidly, and (3) the inorganic P content of sediments increases with decreasing lake volume. Variations in sediment composition also indicate several periods for which productivity in Pyramid Lake may have been elevated over the past 1000 years. Our data provide strong evidence for increased productivity during the first half of the 20th Century, although the typical pattern for cultural eutrophication was not observed. The organic content of sediments also suggests periods of increased productivity in the lake prior to the discovery and development of the region by white settlers. Indeed, a broad peak in organic fractions during the 1800's originates as an increase starting around 1600. However, periods of changing organic content of sediments also correspond to periods when inflow to the lake was probably at extremes (e.g. drought or flood) indicating that fluctuations in river inflow may be an important factor affecting sediment composition in Pyramid Lake.
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    Biogeochemistry 25 (1994), S. 19-39 
    ISSN: 1573-515X
    Keywords: denitrification ; mineralization ; nitrification ; nitrogen ; riparian ; stream ; wetland ; New Jersey ; Pennsylvania ; Pinelands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Denitrification (N2 production) and oxygen consumption rates were measured at ambient field nitrate concentrations during summer in sediments from eight wetlands (mixed hardwood swamps, cedar swamps, heath dominated shrub wetland, herbaceous peatland, and a wetland lacking live vegetation) and two streams. The study sites included wetlands in undisturbed watersheds and in watersheds with considerable agricultural and/or sewage treatment effluent input. Denitrification rates measured in intact cores of water-saturated sediment ranged from ≤ 20 to 260 μmol N m-2 h-1 among the three undisturbed wetlands and were less variable (180 to 260 μmol N M-2 h-1) among the four disturbed wetlands. Denitrification rates increased when nitrate concentrations in the overlying water were increased experimentally (1 up to 770 μM), indicating that nitrate was an important factor controlling denitrification rates. However, rates of nitrate uptake from the overlying water were not a good predictor of denitrification rates because nitrification in the sediments also supplied nitrate for denitrification. Regardless of the dominant vegetation, pH, or degree of disturbance, denitrification rates were best correlated with sediment oxygen consumption rates (r 2 = 0.912) indicating a relationship between denitrification and organic matter mineralization and/or sediment nitrification rates. Rates of denitrification in the wetland sediments were similar to those in adjacent stream sediments. Rates of denitrification in these wetlands were within the range of rates previously reported for water-saturated wetland sediments and flooded soils using whole core15N techniques that quantify coupled nitrification/denitrification, and were higher than rates reported from aerobic (non-saturated) wetland sediments using acetylene block methods.
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    Transport in porous media 16 (1994), S. 237-251 
    ISSN: 1573-1634
    Keywords: phosphate ; soil ; adsorption ; leaching ; kinetics ; computer simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Effects of flow rate and distance travelled on average mobilities of phosphate in a soil are estimated from breakthrough curves of phosphate at the outlets of small columns of soil, following step increases in the concentration at the inlets. Experimental results are compared with results from a computer simulation model of leached columns of soil. Average mobilities of phosphate in columns of soil, following a step increase in the input concentration, decrease with decreasing rate of flow and with increasing distance travelled and appear to be linearly correlated on a logarithmic scale with both flow rate and distance travelled. An empirical equation, describing these relationships, is fitted to data from leaching experiments at flow rates between 30 and 600 cm/day in ≈ 10 cm long columns of soil. Coefficients are obtained by curve fitting breakthrough curves, calculated with a numerical computer simulation model, to experimental breakthrough curves. The fitted equation enables extrapolation to flow rates and travel distances that are more relevant to a field situation.
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    Biogeochemistry 22 (1993), S. 157-178 
    ISSN: 1573-515X
    Keywords: Serengeti ; productivity ; precipitation ; nitrogen ; grazing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract In the Serengeti National Park, Tanzania, precipitation and soil nitrogen vary greatly between northwestern tallgrass areas and southeastern shortgrass areas, with the tallgrass having higher total precipitation and lower soil fertility. We used a model of grassland productivity, carbon/nitrogen cycling, and abiotic factors to test the hypothesis that tallgrass productivity is limited primarily by nitrogen availability while shortgrass productivity is limited by water. Under observed grazing intensities and ungrazed conditions, precipitation exerted primary control over grassland productivity for both regions, with differences in soil texture mediating soil water availability to the grasses. Mineral nitrogen availability interacted with water availability to influence productivity at precipitation levels ⩾ 130% of the mean. Nitrogen mineralization and precipitation were positively related for each grassland type, however, nitrification varied both between grassland types and between grazed and ungrazed conditions. Combined mineralization and nitrification could not maintain soil mineral nitrogen levels in the face of plant nitrogen uptake stimulated by increased precipitation, thus providing the mechanism by which nitrogen becomes a secondary limiting factor for both grasslands. Model experiments indicated that the pattern of primary limitation by precipitation and secondary limitation by nitrogen was robust to model assumptions concerning ungulate deposition of urine and dung nitrogen to the soil.
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    Biogeochemistry 20 (1993), S. 45-62 
    ISSN: 1573-515X
    Keywords: atmospheric deposition ; forest ecosystems ; litter decomposition ; The Netherlands ; nitrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Litterbag experiments were carried out in five forest ecosystems in the Netherlands to study weight loss and nitrogen dynamics during the first two years of decomposition of leaf and needle litter. All forests were characterized by a relatively high atmospheric nitrogen input by throughfall, ranging from 22–55 kg N ha−1 yr−1. Correlation analysis of all seven leaf and needle litters revealed no significant relation between the measured litter quality indices (nitrogen and lignin concentration, lignin-to-nitrogen ratio) and the decomposition rate. A significant linear relation was found between initial lignin-to-nitrogen ratio and critical nitrogen concentration, suggesting an effect of litter quality on nitrogen dynamics. Comparison of the decomposition of oak leaves in a nitrogen-limited and a nitrogen-saturated forest suggested an increased nitrogen availability. The differences in capacities to retain atmospheric nitrogen inputs between these two sites could be explained by differences in net nitrogen immobilization in first year decomposing oak leaves: in the nitrogen-limited oak forest a major part (55%) of the nitrogen input by throughfall was immobilized in the first year oak leaf litter. The three coniferous forests consisted of two monocultures of Douglas fir and a mixed stand of Douglas fir and Scots pine. Despite comparable litter quality in the Douglas fir needles in all sites, completely different nitrogen dynamics were found.
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  • 63
    ISSN: 1573-515X
    Keywords: chronosequence ; montane tropical forest ; nitrogen ; soil development ; phosphorus ; tropical forest
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We determined the effects of nutrient amendments on plant growth in three tropical montane rainforest sites representing a sequence of soil ages (〈 30, 200, and ≈ 2000 y). Factorial fertilization with nitrogen, phosphorus, and all other essential nutrients (combined) was applied to the two younger sites; only nitrogen was applied to the oldest one. Nitrogen supply represented the most important limitation to plant growth in the two younger sites; additions of nitrogen caused significant increases in tree diameter increment, height growth, litterfall, and most other growth-related parameters. In contrast, nitrogen additions had no significant effect on plant growth in the oldest site. Phosphorus additions increased extractable soil phosphorus and plant tissue phosphorus, but did not increase plant growth at the young sites. The results are consistent with Walker & Syers' (1976) model for the control of nutrient limitation during soil development.
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  • 64
    ISSN: 1573-515X
    Keywords: N2O ; CH4 ; red spruce ; balsam fir ; spruce-fir ; forests ; nitrogen ; deposition ; nitrification ; mineralization ; denitrification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured the exchange of N2O and CH4 between the atmosphere and soils in 5 spruce-fir stands located along a transect from New York to Maine. Nitrous oxide emissions averaged over the 1990 growing season (May–September) ranged from 2.1 ug N2O-N/m2-hr in New York to 0.4 ug N2O-N/m2-hr in Maine. The westernmost sites, Whiteface Mtn., New York and Mt. Mansfield, Vermont, had the highest nitrogen-deposition, net nitrification and N2O emissions. Soils at all sites were net sinks for atmospheric CH4 Methane uptake averaged over the 1990 growing season ranged from 0.02 mg CH4-C/M2-hr in Maine to 0.05 mg CH4-C/m2-hr in Vermont. Regional differences in CH4 uptake could not be explained by differences in nitrogen-deposition, soil nitrogen dynamics, soil moisture or soil temperature. We estimate that soils in spruce-fir forests at our study sites released ca. 0.02 to 0.08 kg N2O-N/ha and consumed ca. 0.74 to 1.85 kg CH4 C/ha in the 1990 growing season.
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    Biogeochemistry 15 (1992), S. 213-228 
    ISSN: 1573-515X
    Keywords: immobilization ; leaf litter decomposition ; lignin ; Mediterranean ecosystem ; nitrogen ; tannin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen immobilization in relation to the dynamics of lignin and tannins in nine different types of leaf litter was investigated during a 2-yr study at two Mediterranean ecosystems of SW Spain. Net nitrogen immobilization for all the species was higher in a forest than in the more nutrient-poor soil of a shrubland. Absolute amount of lignin increased in both ecosystems in the first 2–4 months whereas tannin rapidly decreased in the same time period. Increases in lignin were significantly correlated to losses of tannins during decomposition. Initial tannin content was the best predictor of the maximum amount of immobilized nitrogen in litter in both ecosystems. Mechanisms that could explain the immobilization of nitrogen in litter are discussed.
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    Biogeochemistry 18 (1992), S. 19-35 
    ISSN: 1573-515X
    Keywords: Dinitrogen fixation ; nitrogen ; phosphorus ; competition ; legumes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract An analysis of data compiled from the literature confirms a strong inverse relationship between annual rates of nitrogen fixation and the soil nitrogen content in agricultural and pastoral ecosystems. However, this inverse relationship is strongly modified by the rate of application of phosphorus fertilizer, which strongly influences the activities of both symbiotic and non-symbiotic nitrogen fixing organisms. In the case of symbiotic legumes, the response of N-fixation to N and P is in part a result of changes in legume dominance within the plant community. These results, as well as supporting data presented from a review of experiments on nitrogen fixation in a variety of other terrestrial and aquatic ecosystems, provide important support for the hypothesis that phosphorus availability is a key regulator of nitrogen biogeochemistry.
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    Biogeochemistry 18 (1992), S. 1-17 
    ISSN: 1573-515X
    Keywords: microbial biomass-N ; desert ; carbon ; nitrogen ; shrubland ; grassland ; playa
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Microbial biomass nitrogen was measured in unamended (dry) and wetted soils in ten shrubland and grassland communities of the Chihuahuan desert, southern New Mexico, by the fumigation-extraction method. Microbial biomass-N in dry soils was undetectable. Average microbial biomass-N in wetted soils among all plant communities was 15.3 μg g-1 soil. Highest values were found in the communities with the lowest topographic positions, and the minimum values were detected in the spaces between shrubs. Microbial biomass was positively and significantly correlated to soil organic carbon and extractable nitrogen (NH4 + + NO3 -). In a stepwise multiple regression, organic carbon and extractable nitrogen accounted for 40.9 and 5.6%, respectively, of the variance in microbial biomass-N among all the samples. Among communities, the soil microbial biomass was affected by the ratio of carbon to extractable nitrogen. Our results suggest a succession in the control of microbial biomass from nitrogen to carbon when the ratio of carbon to nitrogen decreases during desertification.
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  • 68
    ISSN: 1573-515X
    Keywords: nitrogen ; phosphorus ; soil fertility ; tropical forest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We measured concentrations of soil nutrients (0–15 and 30–35 cm depths) before and after the dry season in control and dry-season irrigated plots of mature tropical moist forest on Barro Colorado Island (BCI) in central Panama to determine how soil moisture affects availability of plant nutrients. Dry-season irrigation (January through April in 1986, 1987, and 1988) enhanced gravimetric soil water contents to wet-season levels (ca. 400 g kg−1 but did not cause leaching beyond 0.8 m depth in the soil. Irrigation increased concentrations of exchangeable base cations (Ca2+, Mg2+, K+, Na+), but it had little effect on concentrations of inorganic N (NH4 +C, NO3 − and S (SO4 2−). These BCI soils had particularly low concentrations of extractable P especially at the end of the dry season in April, and concentrations increased in response to irrigation and the onset of the rainy season. We also measured the response of soil processes (nitrification and S mineralization) to irrigation and found that they responded positively to increased soil moisture in laboratory incubations, but irrigation had little effect on rates in the field. Other processes (plant uptake, soil organic matter dynamics) must compensate in the field and keep soil nutrient concentrations at relatively low levels.
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  • 69
    ISSN: 1573-515X
    Keywords: algae ; nitrogen ; nutrient ; phosphorus ; regeneration ; zooplankton
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Most ecosystem models consolidate members of food-webs, e.g. species, into a small number of functional components. Each of these is then described by a single state variable such as biomass. When a multivariate approach incorporating multiple substances within components is substituted for this univariate one, a ‘stoichiometric’ model is formed. Here we show that the Nitrogen:Phosphorus ratio within zooplankton herbivores varies substantially intraspecifically but not intraspecifically. By using stoichiometric theory and recent measurements of the N:P ratio within different zooplankton taxa, we calculate large differences in ratios of nutrients recycled by different zooplankton species. Finally, we demonstrate that N:P stoichiometry can successfully account for shifts in N- and P-limitation previously observed in whole-lake experiments. Species stoichiometry merges food-web dynamics with biogeochemical cycles to yield new insights.
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    Mathematical geology 23 (1991), S. 325-347 
    ISSN: 1573-8868
    Keywords: hydrocarbons ; kinetics ; inverse methods
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Mathematics
    Notes: Abstract From a determination of the transformation matrix for three pyrolysis product experimental data sets, an examination is given of both the applicability of the laboratory experimental data to the modeling of oil cracking in a sedimentary basin, and of the appropriateness of an inverse model. The results of the laboratory experimental data sets, which were done under different thermodynamic conditions and using different sources, show that the transformation matrix varies over each data set and also with time. Therefore, it is necessary to check the data sets before applying them to a basin for hydrocarbon modeling. The laboratory experimental data taken at lower temperature and over longer times appear more pertinent for the construction of an oil-cracking kinetic model suitable for geologic conditions.
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    Biogeochemistry 12 (1991), S. 129-134 
    ISSN: 1573-515X
    Keywords: biomass burning ; forest soils ; nitrogen ; sulphur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The proportion of total sulphur lost during combustion (600 °C) of Douglas-fir (Pseudotsuga menziesii) foliage is reduced from〉 90% to 65–70% as the SO4-S concentration increases from 10% to 45–50% of the total S content. Foliar SO4-S content is decreased by improvement of plant nitrogen status, suggesting that alterations to soil N availability may influence S transfer to the atmosphere during biomass burning.
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    Biogeochemistry 15 (1991), S. 21-46 
    ISSN: 1573-515X
    Keywords: denitrification ; forest ; nitrification ; nitrogen ; nitrogen mineralization ; N20 ; proton budget ; The Netherlands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Within a long-term research project studying the biogeochemical budget of an oak-beech forest ecosystem in the eastern part of the Netherlands, the nitrogen transformations and solute fluxes were determined in order to trace the fate of atmospherically deposited NH4 + and to determine the contribution of nitrogen transformations to soil acidification. The oak-beech forest studied received an annual input of nitrogen via throughfall and stemflow of 45 kg N ha−1 yr−1, mainly as NH4 +, whereas 8 kg N ha−1 yr−1 was taken up by the canopy. Due to the specific hydrological regime resulting in periodically occurring high groundwater levels, denitrification was found to be the dominant output flux (35 kg N ha−1 yr−1). N20 emmission rate measurements indicated that 57% of this gaseous nitrogen loss (20 kg N ha−1 yr−1) was as N2O. The forest lost an annual amount of 11 kg N ha−1 yr−1 via streamwater output, mainly as N03 −. Despite the acid conditions, high nitrification rates were measured. Nitrification occurred mainly in the litter layer and in the organic rich part of the mineral soil and was found to be closely correlated with soil temperature. The large amount of NH4 + deposited on the forest floor via atmospheric deposition and produced by mineralization was to a large extent nitrified in the litter layer. Almost no NH4 + reached the subsurface soil horizons. The N03 − was retained, taken up or transformed mainly in the mineral soil. A small amount of N03 − (9 kg N ha−1 yr−1) was removed from the system in streamwater output. A relatively small amount of nitrogen was measured in the soil water as Dissolved Organic Nitrogen. On the basis of these data the proton budget of the system was calculated using two different approaches. In both cases net proton production rates were high in the vegetation and in the litter layer of the forest ecosystem. Nitrogen transformations induced a net proton production rate of 2.4 kmol ha−1 yr−1 in the soil compartment.
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    Biogeochemistry 12 (1991), S. 135-148 
    ISSN: 1573-515X
    Keywords: fens ; management ; nitrogen ; phosphorus ; productivity ; vegetation ; wetlands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A fertilization experiment was carried out in 3 mesotrophic fens to investigate whether plant growth in these systems is controlled by the availability of N, P or K. The fens are located in an area with high N inputs from precipitation. They are annually mown in the summer to prevent succession to woodland. Above-ground plant biomass increased significantly upon N fertilization in the two “mid”-succession fens studied. In the “late”-succession fen that had been mown for at least 60 years, however, plant biomass increased significantly upon P fertilization. The mowing regime depletes the P pool in the soil, while it keeps N inputs and outputs in balance. A long-term shift occurs from limitation of plant production by N toward limitation by P. Hence, mowing is a suitable management tool to conserve the mesothrophic character of the fens.
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  • 74
    ISSN: 1573-515X
    Keywords: atmospheric deposition ; nitrogen ; nutrient cycling ; spruce decline ; subalpine spruce-fir
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Nitrogen inputs, fluxes, internal generation and consumption, and outputs were monitored in a subalpine spruce-fir forest at approximately 1000-m elevation on Whiteface Mountain in the Adirondacks of New York, USA. Nitrogen in precipitation, cloudwater and dry deposition was collected on an event basis and quantified as an input. Throughfall, stemflow, litterfall and soil water were measured to determine fluxes within the forest. Nitrogen mineralization in the forest floor was estimated to determine internal sources of available N. Lower mineral horizon soil water was used to estimate output from the ecosystem. Vegetation and soil N pools were determined. During four years of continuous monitoring, an average of 16 kg N ha−1 yr−1 was delivered to the forest canopy as precipitation, cloudwater and dry deposition from the atmosphere. Approximately 30% of the input was retained by the canopy. Canopy retention is likely the result of both foliar uptake and immobilization by bark, foliage and microorganisms. Approximately 40 kg of N was made available within the forest floor from mineralization of organic matter. Virtually all the available ammonium (mineralized plus input from throughfall) is utilized in the forest floor, either by microorganisms or through uptake by vegetation. The most abundant N component of soil water solutions leaving the system was nitrate. Net ecosystem fluxes indicate accumulation of both ammonium and nitrate. There is a small net loss of organic N from the ecosystem. Some nitrate leaves the bottom of the B horizon throughout the year. Comparisons with other temperate coniferous sites and examination of the ecosystem N mass balance indicate that N use efficiency is less at our site, which suggests that the site is not severely limited by N.
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    Journal of atmospheric chemistry 12 (1991), S. 137-151 
    ISSN: 1573-0662
    Keywords: Soot particles ; polycyclic aromatic hydrocarbons ; NO2 ; HNO3 ; heterogeneous reactions ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract An experimental technique for studying atmospheric heterogeneous reactions of polyaromatic hydrocarbons (PAH) on particle surfaces is reported. Particle bound organics were reacted in a 200 liter Teflon continuous stirred tank reactor (CSTR), with vapor phase oxidants. To provide a source of chemically stable particles for the CSTR, soot particles from a residential wood stove were first introduced during under darkness into a 25 m3 outdoor Teflon chamber. Air containing the particles was then added at a constant flow to the CSTR. The rates of heterogeneous reactions were obtained by comparing reacted particle samples with unreacted ones. The derivation of rate expressions for heterogeneous reactions in the CSTR is described. The use of the technique for a study of the nitration of selected soot particle bound PAH species by NO2 and HNO3 is demonstrated.
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  • 76
    ISSN: 1573-0662
    Keywords: Organic nitrates ; kinetics ; OH radical ; atmosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique. The following rate coefficients (in units of 10-12 cm3 molecule-1 s-1) were obtained: 1,2-propandiol dinitrate, 〈0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; α-nitrooxyacetone, 〈0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50. The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered.
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    Journal of paleolimnology 4 (1990), S. 1-22 
    ISSN: 1573-0417
    Keywords: sulfate ; carbon ; nitrogen ; hydrogen ; organic matter ; enrichment factor ; lake sediments ; paleolimnology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract This paper discusses the use of S as a paleolimnological tracer of limnetic sulfate concentration. A positive relationship (p〈0.05) was found between limnetic sulfate and sediment S concentrations for the Great Lakes, English Lakes, and lakes from the Adirondack and Northern New England regions. There is a positive correlation (p〈0.05) between C and S concentration in sediment across all regions studied. The importance of C in affecting S content in sediment was also examined by a series of cores taken at different water depths in Big Moose Lake (Adirondacks). There was a strong relationship between C and S among cores with sediment from deeper water having higher C and S concentrations (r 2=0.99). Sulfur from the shallower cores had greater concentrations of chromium-reducible S (pyrite), while cores from deeper waters had a greater proportion of organic S fractions including C-bonded S and ester sulfates. For assessing historical changes in S accumulation in sediments, enrichment factors were calculated for the PIRLA lakes. Pre-1900 net sediment accumulation rates of S were very similar across all regions. Sulfur enrichment was greatest in Adirondack sediment which had total post-1900 S accumulation of 1.1 to 7.4 times pre-1900 S accumulation. Sediment from Northern New England (NNE) generally had lower S concentration than Adirondack sediments and S enrichment factors ranged from 1.2 to 2.1. Sediment from the Northern Great Lakes States region had similar S concentration and distribution with depth to NNE sediment. In two Northern Florida lakes, sediment showed little variation in S concentration with depth, but in two other lakes from the same region, there was higher S concentration in deeper layers. Lakes which had the greatest enrichment factors also exhibited the most marked changes in C:S ratios. Ratios of C:N showed little variation (10.6 to 26.1) among the PIRLA lakes. A first order model indicated slow decomposition within these organic rich sediments. Elemental concentrations and ratios of sediment from a variety of lakes and reservoirs were complied. Maximum and minimum elemental ratios for all the data were 28 to 8.1 for C:N, 0.81 to 0.11 for C:H, and 675 to 12.5 for C:S, respectively. For the C:S ratios in all regions except the Great Lakes, the maximum ratio was less than 231. Both the maximum and minimum amount of N and H concentration of organic matter is related to biotic processes. The minimum concentration of S is regulated not only by nutrient demands but also by non-assimilatory processes. Sulfur incorporation into sediments is a function of a complex of factors, but limnetic sulfate concentration and organic matter content play a major role in regulating the S content of sediment. Further quantification of S incorporation pathways will aid in the paleolimnological interpretation of sediment S profiles. Such information is also important in assessing how S sediment pools will respond to decreases in limnetic sulfate concentration which may occur with decreases in inputs from acidic deposition.
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    Biogeochemistry 10 (1990), S. 67-79 
    ISSN: 1573-515X
    Keywords: deserts ; ecosystem ; nitrogen ; nutrient cycling ; soils ; southwestern United States
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A lower limit for nitrogen loss from desert ecosystems in the southwestern United States was estimated by comparing nitrogen inputs to the amount of nitrogen stored in desert soils and vegetation. Atmospheric input of nitrogen for the last 10 000 years was conservatively estimated to be 2.99 kg N/m2. The amount of nitrogen stored in desert soils was calculated to be 0.604 kg N/m3 using extant data from 212 profiles located in Arizona, California, Nevada, and Utah. The average amount of nitrogen stored in desert vegetation is approximately 0.036 kg N/m2. Desert conditions have existed in the southwestern United States throughout the last 10 000 years. Under such conditions, vertical leaching of nitrogen below a depth of 1 m is small (ca. 0.028 kg N/m2 over 10 000 years) and streamflow losses of nitrogen from the desert landscape are negligible. Thus, the discrepancy found between nitrogen input and storage represents the amount of nitrogen lost to the atmosphere during the last 10 000 years. Loss of nitrogen to the atmosphere was calculated to be 2.32 kg N/m2, which is 77% of the atmospheric inputs. Processes resulting in nitrogen loss to the atmosphere from desert ecosystems include wind erosion, ammonia volatilization, nitrification, and denitrification. Our analysis cannot assess the relative importance of these processes, but each is worthy of future research efforts.
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    Biogeochemistry 11 (1990), S. 1-22 
    ISSN: 1573-515X
    Keywords: disturbance ; ecosystems ; forests ; indirect interactions ; landscape ecology ; Minnesota ; nitrogen ; nutrient cycling ; path analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Path analysis was used to determine the importance of long-term disturbance regime and the relative importances of correlations among vegetation patterns, disturbance history, and nitrogen (N) mineralization in old-growth forests of northwestern Minnesota. Leaf biomass (estimated by allometric equations), fire history (from fire scars on Pinus resinosa trees), and N mineralization rates (estimated from incubationsin situ) were determined from sample plots dominated by Betula papyrifera, Populus tremuloides, andP. grandidentata a mixture ofAcer saccharumandTilia americana, or Quercus borealis andOstrya virginiana. Results showed that topographic and soil-moisture controls on N mineralization, vegetation patterns, and disturbance are substantially stronger than is suggested by direct correlation. Indirect interactions among ecosystem variables played in important role. These interactions probably include the tendency for species that cycle large amounts of N to colonize more mesic sites that burned rarely in the past. Soil moisture was correlated both directly with N mineralization and indirectly, through its effects on vegetation pattern, and thus, litter quality. Although disturbance regime also depended on topography, the strengths of relationships between disturbance regime and other variables were relatively weak. These dependencies suggested that long-term fire regime is probably more a consequence than a cause for vegetation and fertility patterns. Topography, through its effects on soil moisture and microclimate, is an overriding influence on ecosystem properties, which in turn influence fire regime.
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  • 80
    ISSN: 1573-515X
    Keywords: cumulative ; flow ; GIS ; landscape ; lead ; nitrogen ; phosphorus ; suspended solids ; watershed ; wetlands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A method was developed to evaluate the cumulative effect of wetland mosaics in the landscape on stream water quality and quantity in the nine-county region surrounding Minneapolis—St. Paul, Minnesota. A Geographic Information System (GIS) was used to record and measure 33 watershed variables derived from historical aerial photos. These watershed variables were then reduced to eight principal components which explained 86% of the variance. Relationships between stream water quality variables and the three wetland-related principal components were explored through stepwise multiple regression analysis. The proximity of wetlands to the sampling station was related to principal component two, which was associated with decreased annual concentrations of inorganic suspended solids, fecal coliform, nitrates, specific conductivity, flow-weighted NH4 flow-weighted total P, and a decreased proportion of phosphorus in dissolved form(p 〈 0.05). Wetland extent was related to decreased specific conductivity, chloride, and lead concentrations. The wetland-related principal components were also associated with the seasonal export of organic matter, organic nitrogen, and orthophosphate. Relationships between water quality and wetlands components were different for time-weighted averages as compared to flow-weighted averages. This suggests that wetlands were more effective in removing suspended solids, total phosphorus, and ammonia during high flow periods but were more effective in removing nitrates during low flow periods.
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    Biogeochemistry 11 (1990), S. 23-43 
    ISSN: 1573-515X
    Keywords: acid precipitation ; ammonium ; mass balance ; nitrate ; nitrogen ; retention
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The relative contribution of HN03 to precipitation acidity in eastern Canada has increased in recent years leading to some concern that the relative importance of NO− 3 deposition in acidification of terrestrial and aquatic ecosystems may increase. To gauge the extent of this impact, annual mass balances for N0− 3 and NH+ 4 were calculated for several forested catchments and lakes in Ontario. Retention of NH+ 4 (R NH4) by forested catchments was consistently high compared to retention of NO3 − (R NO3) which was highly variable. Retention of inorganic nitrogen was influenced by catchment grade and areal water discharge. In lakes, the reciprocals of retention of N0− 3 and NH+ 4 were linearly related to the ratio of lake mean depth to water residence time (z/τ; equal to areal water discharge), and retention did not appear to be a function of degree of acidification of the lakes. Net N consumption-based acidification of lakes, defined as the ratio of annual NH; mass to N0− 3 mass consumption, was negatively correlated with /τ and N consumption-related acidification was most likely to occur when − was 〈 1.5 m yr−1. If retention mechanisms are unaffected by changes in deposition, changes in deposition will still result in changes in surface water concentrations although the changes will be of similar proportions. Therefore, ‘NO− 3 saturation’ should not be defined by concentrations alone, but should be defined as decreasing long-term, average NO− 3 retention in streams and lakes in response to long-term increases in NO− 3 deposition. Analysis o f survey data will be facilitated by grouping lakes and catchments according to similar characteristics.
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  • 82
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    Keywords: nitrogen ; snow ; flux
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Increased emissions of nitrogen compounds to the atmosphere by human activities have been well documented. However, in order to better quantify these anthropogenic emissions, better knowledge of natural emissions rates must be known. In addition, variation in natural emissions through time should be documented. In this note we present data collected and/or analyzed by us for NO3 − in recent snow from remote regions of the world. We also summarize existing data sets from other remote regions. This is done to establish a better understanding of NO3 − deposition rates in these regions as well as to add more information to our global understanding of NO3 − deposition.
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    Biogeochemistry 9 (1990), S. 117-134 
    ISSN: 1573-515X
    Keywords: nitrogen ; Mediterranean ; natural versus anthropogenic atmospheric nitrogen ; atmospheric input ; riverine input ; marine ecosystems ; primary production
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Bulk inorganic nitrogen deposition was monitored over a period of 3 years at the Bavella Pass (Corsica, France). Annual fluxes range between 126 and 150μmol.m−2.d-−1, increasing slightly with annual rainfall. Natural background average concentrations of rain water and associated fluxes were estimated from a classification of rain events into ‘natural’ (Oceanic and Saharan), polluted and composite. Long range transport of incoming polluted air masses increases the atmospheric wet nitrogen input by at least a factor of 1.6 in this Mediterranean area. Extrapolation of atmospheric dissolved inorganic nitrogen input to the Western Mediterranean leads to fluxes of 80 to l00μmol.m−2.d-−1. This atmospheric input is in the same order of magnitude as the inorganic nitrogen riverine input. As a consequence, the nitrogen budget for the Mediterranean has had to be reassessed. Atmospheric wet inorganic nitrogen input is of noticeable importance to marine Mediterranean ecosystems, representing on average 10 to 25% of new production in the Western Basin, with values of up to 60% in oligotrophic zones.
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    Journal of atmospheric chemistry 11 (1990), S. 255-269 
    ISSN: 1573-0662
    Keywords: NH3 ; NO2 ; O3 ; N2O formation ; kinetics ; nighttime NO2 oxidation ; heterogeneous reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract In a nighttime system and under relatively dry conditions (about 15 ppm H2O), the reaction mixture of NO2, O3, and NH3 in purified air turns out to result in the formation of nitrous oxide (N2O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm. N2O is thought to arise through the heterogeneous reaction of gaseous N2O5 and absorbed NH3 at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\] In principle, there is competition between this reaction and that of adsorbed H2O with N2O5, resulting in the formation of HNO3. At high water concentrations (RH〉75%), no formation of N2O was found. Although the rate constant of adsorbed NH3 with gaseous N2O5 is much larger than that of the reaction of adsorbed H2O with gaseous N2O5, the significance of the observed N2O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H2O and NH3 on a surface. A number of NH3 and H2O adsorption measurements on several materials are discussed.
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    Biogeochemistry 10 (1990), S. 1-28 
    ISSN: 1573-515X
    Keywords: boreal forest ; decomposition ; litter quality ; nitrogen ; productivity ; soil temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A model of boreal forest dynamics was adapted to examine the factors controlling carbon and nitrogen cycling in the boreal forests of interior Alaska. Empirical relationships were used to simulate decomposition and nitrogen availability as a function of either substrate quality, the soil thermal regime, or their interactive effects. Test comparisons included black spruce forests growing on permafrost soils and black spruce, birch, and white spruce forests growing on permafrost-free soils. For each forest, simulated above-ground tree biomass, basal area, density, litterfall, moss biomass, and forest floor mass, turnover, thickness, and nitrogen concentration were compared to observed data. No one decay equation simulated forests entirely consistent with observed data, but over the range of upland forest types in interior Alaska, the equation that combined the effects of litter quality and the soil thermal regime simulated forests that were most consistent with observed data. For black spruce growing on permafrost soils, long-term simulated forest dynamics in the absence of fire resulted in unproductive forests with a thick forest floor and low nitrogen mineralization. Fires were an important means to interrupt this sequence and to restart forest succession.
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    Biogeochemistry 8 (1989), S. 185-204 
    ISSN: 1573-515X
    Keywords: phosphorus ; nitrogen ; wetlands ; beaver ponds ; conifer swamp ; sedge fen ; Precambrian shield ; nutrient retention ; mass balance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Phosphorus and nitrogen mass balances of five wetlands (two beaver ponds, two conifer-Sphagnum swamps and one sedge fen) situated in three catchments in central Ontario, Canada, were measured. Monthly and annual input-output budgets of total phosphorus (TP), total nitrogen (TN), total organic nitrogen (TON), total inorganic nitrogen (TIN), ammonium ion (NH4 + -N), nitrate (NO 3 − -N) and dissolved organic carbon (DOC) were estimated for the five wetlands during the 1982–83 and 1983–84 water years. Except for the deepest beaver pond (3.2 m) which had annual TP retention of −44% (−0.030 ± 0.015 g m−2 yr−1), the wetlands retained 〈 0.001 to 0.015 g M−2 yr−1 ; however, this wasless than 20% of the inputs and the estimated budget uncertainties were equal to or greater than the retention rates. Annual TN retentions ranged from −0.44 to 0.56 g m−2 yr−1 (−12 to 4%) but were not significantly different from zero. The wetlands transformed nitrogen by retaining TIN (16 to 80% RT) and exporting an equivalent amount as TON (−7 to 102% RT). The beaver ponds, however, retained NO 3 − while NH 4 + was passed through or the outputs exceeded the inputs. In contrast, the conifer swamps retained both NH 4 + and NO 3 − . DOC fluxes into and out of the beaver ponds were equal (−18 and 4% RT) but output from the conifer swamps exceeded input by 〉 90%. Marked seasonal trends in nutrient retention were observed. Nutrient retention coincided with low stream flow, increased evapotranspiration and biotic uptake during the summer. Net nutrient export occurred during the winter and spring when stream flows were highest and biotic uptake was low.
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    Pure and applied geophysics 127 (1988), S. 529-544 
    ISSN: 1420-9136
    Keywords: Ionosphere ; nitrogen ; vibrational temperatures ; N2 and CO2 and populations of N2 and CO2 in the D, E and F regions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Theoretical and experimental aspects of the production, transformation, diffusion and loss of N2 in the upper atmosphere are considered. The N2-CO2 near-resonant system in theD andE regions is taken into account. We describe our understanding of the methods necessary to find the vibrational populations of N2 and CO2 (asymmetric mode of CO2). The calculations of the vibrational temperatures in theD, E, andF regions for the mid-latitude ionosphere and an aurora are presented. The connection between the excited species and the 4.26-μm radiation intensities is considered. The models for the rate coefficient of the reaction of O+ with N2 and the electron density decrease resulting from N2 in the F region are discussed.
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    Biogeochemistry 5 (1988), S. 109-131 
    ISSN: 1573-515X
    Keywords: soil organic matter ; nitrogen ; phosphorus ; sulfur ; simulation ; grasslands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We have developed a model to simulate the dynamics of C, N, P, and S in cultivated and uncultivated grassland soils. The model uses a monthly time step and can simulate the dynamics of soil organic matter over long time periods (100 to 10,000 years). It was used to simulate the impact of cultivation (100 years) on soil organic matter dynamics, nutrient mineralization, and plant production and to simulate soil formation during a 10,000 year run. The model was validated by comparing the simulated impact of cultivation on soil organic matter C, N, P, and S dynamics with observed data from sites in the northern Great Plains. The model correctly predicted that N and P are the primary limiting nutrients for plant production and simulated the response of the system to inorganic N, P, and S fertilizer. Simulation results indicate that controlling the C:P and C:S ratios of soil organic matter fractions as functions of the labile P and S levels respectively, allows the model to correctly simulate the observed changes in C:P and C:S ratios in the soil and to simulate the impact of varying the labile P and S levels on soil P and S net mineralization rates.
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    Biogeochemistry 6 (1988), S. 31-43 
    ISSN: 1573-515X
    Keywords: nitrogen ; phosphorus ; mineralization ; productivity ; peatlands
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Release of inorganic nitrogen and phosphorus in the soil of a peatland (fen) in The Netherlands was measured by means of an in situ incubation technique. Three sampling stations were chosen along a gradient in the plant productivity and water chemistry of the fen. The station with the highest biomass production was located near the ditch that supplied the fen with water in amounts matching water losses through evaporation and downward percolation to the groundwater. Water chemistry at this station strongly resembled that of the ditch water. The two stations remote from the ditch had much lower plant biomass, and significantly lower pH, conductivity, and calcium and bicarbonate concentrations. The vegetation at these two stations was characterized by a thick Sphagnum carpet. The release of inorganic N and P was much faster at the two stations remote from the ditch than at that located near the ditch. The differences in mineralization rate are probably due to the differences in water chemistry; phosphates are more soluble at low than at high pH. The fast N mineralization at stations with a thick Sphagnum carpet may be related to the chemical composition of Sphagnum litter. The difference in productivity is not explained by the N and P mineralization rates. Direct supply of N and P from the ditch are probably the main cause of the high productivity at the station bordering the ditch.
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    Biogeochemistry 4 (1987), S. 77-90 
    ISSN: 1573-515X
    Keywords: Chesapeake Bay ; nutrients ; eutrophication ; estuary ; nitrogen ; phosphorus ; silicon ; sediments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Recently published annual mass balances or budgets for nitrogen, phosphorus, and silicon in Chesapeake Bay have pictured the estuary as retaining a very large fraction, perhaps all, of the nutrients that enter from land drainage, the atmosphere, and anthropogenic discharges. However, these budgets have been based on estimates of the net exchanges of nutrients at the mouth of the bay or on the rates of accumulation of nutrients and sediments calculated from the distributions of various geochemical tracers in the sediments. While conceptually straightforward, the first approach is subject to large errors because it requires the determination of a small "signal" against a large background of tidal "noise". The second approach has led to overestimates of the nutrient trapping efficiency of the bay because tracer-derived sediment deposition rates have been multiplied by the surface area of the whole bay or various parts of the bay rather than by the smaller area of active sediment deposition. This approach is also incorrect because the average, long-term rates of sediment deposition measured by the geochemical tracers, including major floods, have been compared to shorter-term records of nutrient input. The more appropriate calculation of nutrient retention based on contemporaneous measurements of nutrient and sediment input and the chemical compositon of sediments accumulated in the estuary shows that Chesapeake Bay retains only some 3–6% of the nitrogen, 11–17% of the phosphorus and 33–83% of the silicon brought into its waters during a year in which no major flood occurred. This behavior suggests that current problems of estuarine eutrophication are more a consequence of present nutrient inputs than an inevitable or inescapable legacy of past enrichment. It also follows that the management or manipulation of nutrient loadings to esturies may lead to a more rapid response in environmental quality than previously predicted.
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    Biogeochemistry 4 (1987), S. 3-14 
    ISSN: 1573-515X
    Keywords: nutrient dynamics ; sediments ; ground water ; phosphorus ; nitrogen ; organic matter
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A small pond in southwestern peninsular Florida was sampled to determine the areal and depth distribution of total phosphorus, total nitrogen, and organic matter. Concentrations of these constituents decreased from the center to the edge of the pond and from the top to the bottom of the sediments. At the center of the pond total phosphorus showed a secondary concentration peak at a depth of 20 to 40 cm in the sediments indicative of the downward transfer of soluble phosphorus during times of low water. A system of monitoring wells was installed at the pond to measure groundwater input and output nutrient concentrations. There was no difference in total groundwater nitrogen concentration across the pond but the mean increase in total phosphorus concentration between input and output wells, ca. 200 μg1−1, was statistically highly significant. The results suggest that whereas nitrogen is recycled from sediments to the pond and the atmosphere, the pond-sediment system loses some phosphorus to groundwater throughflow.
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    Biogeochemistry 2 (1986), S. 3-27 
    ISSN: 1573-515X
    Keywords: Carbon ; climate ; forests ; landscape ecology ; nitrogen ; productivity ; soil moisture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The interactions between the biotic processes of reproduction, growth, and death and the abiotic processes which regulate temperature and water availability, and the interplay between the biotic and abiotic processes regulating N and light availabilities are important in the dynamics of forest ecosystems. We have developed a computer simulation that assembles a model ecosystem which links these biotic and abiotic interactions through equations that predict decomposition processes, actual evapo-transpiration, soil water balance, nutrient uptake, growth of trees, and light penetration through the canopy. The equations and parameters are derived directly from field studies and observations of forests in eastern North America, resulting in a model that can make accurate quantitative predictions of biomass accumulation, N availability, soil humus development and net primary production.
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    Biogeochemistry 2 (1986), S. 53-65 
    ISSN: 1573-515X
    Keywords: Chaparral conversion ; nitrogen ; nitrate ; soil water ; stream water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract An Arizona watershed converted from chaparral to grass, released high concentrations of nitrate to stream water. The nitrate originated from the rooting zone of the decomposing shrubs. High nitrate concentrations (44–373 ppm) were found in soil solutions from 1.5-, 3.0-, and 4.6-m depths on the converted watershed as compared with low nitrate concentrations (0.2–6.2 ppm) found in an adjacent undisturbed area. Soil solution nitrate concentrations at the 0.3-m depth were generally low, especially in the untreated area. High nitrate concentrations were balanced mainly by relative decreases in bicarbonate anions in the soil solutions and in the stream water. Multiple stepwise regression analyses showed improvement in the regression of bicarbonate on nitrate when chloride and sulfate anions were entered as variables.
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  • 94
    ISSN: 1573-515X
    Keywords: sulfur ; carbon ; nitrogen ; mineralization ; simulation model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The dynamics of sulfur immobilization and mineralization in soil were simulated to test hypotheses about their regulation by the availability of carbon and nitrogen. The concept of chemical bond classes was incorporated into the model to account for variation in composition of carbon, nitrogen, and sulfur compounds. Microbial biomass was differentiated into bacteria and fungi, and the element ratios of both groups were assumed to vary. Organic residues were divided between dead microbes plus microbial products, and the more labile fraction of stabilized soil organic matter. Concepts and hypotheses in the model were tested by applying it to data on microbial biomass, sulfate, nitrate, and CO2 evolution obtained in laboratory incubations of two soils amended with sulfate and cellulose. An important mechanism of regulation tested in the model was the stimulation of sulfohydrolase enzyme production depending on sulfur stress in microbial biomass. The hypothesis that excess sulfate is stored as ester sulfate was supported by model dynamics.
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    Biogeochemistry 2 (1986), S. 149-161 
    ISSN: 1573-515X
    Keywords: Microbial manganese(II) oxidation ; manganese(II) oxidation ; kinetics ; bacteria ; O2H2S interface 04
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A great number of important chemical reactions that occur in the environment are microbially mediated. In order to understand the kinetics of these reactions it is necessary to develop methods to directly measure in situ reaction rates and to develop models to help elucidate the mechanisms of microbial catalysis. The oxidation of Mn(II) in a zone above the O2/H2S interface in Saanich Inlet, B.C., Canada is one such reaction. We present here a method by which in situ rates of microbial Mn(II) oxidation are measured and a model based on our experimental results to describe the general mechanism of Mn(H) oxidation. We propose a two step process in which Mn(II) is first bound by a site on the bacterial surface and then oxidized. The model is analogous to the Langmuir isotherm model for surface catalyzed gas reactions or the Michaelis-Menten model for enzyme kinetics. In situ Mn(II) oxidation rates were measured during five cruises to Saanich Inlet during the summers of 1983 and 1984. We use the model to calculate the apparent equilibrium binding constant (Ks ≈ 0.18 μM), the apparent half saturation constant for biological Mn(H) oxidation (Km = 0.22 to 0.89 μM), the maximum rate of Mn(II) oxidation (Vmax = 3.5 to 12.1 nM·h-1) and the total microbial surface binding site concentration (Σ E ≈ 51 nM). Vmax for Mn(II) oxidation agrees with the rates calculated from the value of the flux of Mn(II) to the oxidizing zone using the Mn(II) gradient and estimates of the eddy diffusion coefficient. This consistancy verifies our methodology and indicates that the rate of Mn(II) oxidation is nearly equal to the (Vmax for the reaction. We conclude that in this environment the Mn(II) oxidation rate is more a function of the total number of surface binding sites than the Mn(H) concentration.
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  • 96
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    Springer
    Journal of atmospheric chemistry 4 (1986), S. 241-251 
    ISSN: 1573-0662
    Keywords: Free radical reactions ; kinetics ; product distribution ; methane oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Formation of methoxy (CH3O) radicals in the reaction (1) CH3O2+NO→CH3O+NO2 at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH3O2 and CH3ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k 1 is (7±2) 10-12 cm3/molecule · s in good agreement with previous results.
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  • 97
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    Springer
    Biogeochemistry 2 (1986), S. 313-328 
    ISSN: 1573-515X
    Keywords: soil organic sulfur ; mineralization ; reaction rates ; kinetics ; immobilization ; soil adsorption ; sulfate ; first-order ; michaelis-menten
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Transformations of organic and inorganic S in two forested Spodosols from the Hubbard Brook Experimental Forest, New Hampshire and the Huntington Forest in the Adirondack Mts. of New York were investigated using laboratory35SO4 2- incorporation experiments. Sulfur transformations were modeled as a set of three reversible, first-order reactions in which soluble SO 4 2- is converted to adsorbed SO 4 2- , ester sulfate and carbon-bonded S. Reaction rate contants for35SO 4 2- adsorption/desorption and immobilization reactions involving ester sulfate and carbon-bonded S were determined using a fifth order Runge-Kutta-Fehlberg integration routine combined with least squares fitting. Model simulations were able to account for over 93% of the variation in the distribution of35S in S fractions. A hypothetical application of immobilization rate constants to field situations at the Hubbard Brook Experimental Forest suggests that large quantities of S cycle through organic forms in Northern Hardwood Forest Ecosystems.
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  • 98
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    Electronic Resource
    Springer
    Biogeochemistry 1 (1985), S. 233-256 
    ISSN: 1573-515X
    Keywords: Lake ; nutrients ; phosphorus ; nitrogen ; cycling ; river
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Lake Vanda is a permanently ice covered, meromictic, closed basin lake, located in the Dry Valley region of Southern Victoria Land, Antarctica. A unique feature of the lake water column structure is that the bottom lake waters exist as a natural diffusion cell. The diffusive nature of these waters allows rates of sulfate reduction, nitrification and denitrification to be calculated from nutrient concentration gradients. Calculation reveals that sulfate reduction is by far the most important anoxic process acting to oxidize organic material. In addition, rate calculations reveal that bottom water nutrient profiles are in steady state. One argument in support of this conclusion is that the calculated rate of nitrification balances the flux of ammonia from the anoxic lake waters. The flux of phosphorus from the reducing waters is several times less than would be predicted from the nitrogen and phosphorus content of decomposing lake seston. Solubility calculations show that phosphorus may be actively removed at depth in Lake Vanda by the formation of hydroxyapatite. It is found that estimated rates of nitrogen and phosphorus removal in the bottom lake waters and sediments roughly balance the riverine input flux. This suggests that throughout the lake a nutrient steady state may exist, and that the anoxic zone may be the most important loci for nutrient removal. Finally, the ratio of nitrogen to phosphorus entering Lake Vanda by riverine input is less than the ‘Redfield’ ratio of 16/1; in contrast to the lake waters which are strongly phosphorus limited at all depths. This curious aspect of the lake's nutrient chemistry is explained by the presence of preformed nitrogen, which has been concentrated in the deep brine due to several episodes of evaporative concentration.
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  • 99
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    Springer
    Journal of atmospheric chemistry 2 (1985), S. 359-375 
    ISSN: 1573-0662
    Keywords: Photochemistry ; kinetics ; ozone decomposition ; iodine atoms ; IO radicals ; iodine oxides ; atmospheric iodine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The I-atom sensitised decomposition of ozone in air at 1 atm pressure and ambient temperature has been investigated. Iodine atoms were produced by photolysis of I2 using visible light or of CH3I using ultraviolet light. In both cases, the quantum yield for O3 decomposition was 1.25 (±0.11) per I atom. An important role is proposed for the self-reaction of IO radicals leading to higher oxides of iodine, IO+IO(+M)→I2O2(+M)→higher oxides, which predominated over the bimolecular reaction leading to regeneration of I atoms, IO+IO→2I+O2, with k 2a/k 2b≥4. Simple computer modelling calculations indicate that reaction (2a) may be important in determining the fate of photolabile iodine species in the atmosphere. The consequences for the behaviour of radioiodine releases are also discussed.
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