Sources of dissolved organic matter (DOM) in a Rocky Mountain stream using chemical fractionation and stable isotopes

Dissolved organic matter (DOM) is an important vehicle for the movement of nutrients from terrestrial to aquatic systems. To investigate how the source and composition of aquatic DOM change in both space and time, we used chemical, spectroscopic, and isotopic analyses to characterize DOM in a headwater catchment in the Colorado Front Range. Streamwater samples for DOM analyses were collected from 2 sites, a lightly vegetated alpine site and a forested, subalpine site, in the North Boulder Creek catchment during the snowmelt runoff season (May–September). Concentrations of dissolved organic carbon (DOC) peaked on the ascending limb of the snowmelt hydrograph at both the alpine (2.6 mg C l⁻¹) and the subalpine sites (7.0 mg C l⁻¹) and decreased sharply on the descending limb of the hydrograph. Fractionation of DOM into operationally defined humic and non-humic components showed that the fulvic acid content of DOC decreased through the season at both sites and that spectroscopic (fluorescence and ultraviolet) properties of the humic DOM fraction shifted in a manner consistent with an increase in the proportion of humic DOM derived from instream sources as compared to terrestrial catchment sources. Humic and non-humic fractions of DOM isolated near peak flow in June and during low flows in September showed a seasonal enrichment in ¹⁵N and ¹³C as well as a seasonal decrease in the ratio of aromatic to aliphatic carbon, both of which were correlated with a decrease in the C:N ratio of the DOM fractions. These results suggest that seasonal shifts in the isotopic and chemical characteristics of DOM are a result of changes in catchment sources of DOM. In particular, it appears that DOM production in alpine lakes is an important contributor to the streamwater DOM load during late season low flows, especially in the alpine reach of the catchment. Our results further suggest that stable isotopes of C and N are useful tools, particularly when combined with ancillary data such as elemental analyses and catchment discharge, for evaluating sources and transformations of DOM at the catchment scale.     

Chemical and seasonal controls on the dynamics of dissolved organic matter in a coniferous old-growth stand in the Pacific Northwest,USA

Soil organic matter (SOM) is the largest terrestrial C pool, and retention and release of dissolved organic matter (DOM) cause formation and loss of SOM. However, we lack information on how different sources of DOM affect its chemical composition, and how DOM chemical composition affects retention. We studied seasonal controls on DOM production and chemical controls on retention in soils of a temperate coniferous forest. The O horizon was not usually the dominant source for dissolved organic C (DOC) or N (DON) as has been reported for other sites. Rather, net production of both DOC and DON was often greater in the shallow mineral soil (0–10 cm) than in the O horizon. DOM production in the shallow mineral soil may be from root exudation as well as turnover of fine roots and microflora in the rhizosphere. In the field, the two acid fractions (hydrophobic and hydrophilic acids) dominated the soil solution at all depths. A major portion of net production and removal of total DOC within the soil column was explained by increases and decreases in these fractions, although a shift in chemical composition of DOM between the O and mineral soil horizons suggested different origins of DOM in these layers. A larger loss of the free amino fraction to deep soil water at this study site than at other sites suggested lower retention of labile DON. Field DOM removal measurements suggest that field-measured parameters may provide a good estimate for total DOM retained in mineral soil.     

Landscape Controls on Organic and Inorganic Nitrogen Leaching across an Alpine/Subalpine Ecotone,Green Lakes Valley,Colorado Front Range

Here we report measurements of organic and inorganic nitrogen (N) fluxes from the high-elevation Green Lakes Valley catchment in the Colorado Front Range for two snowmelt seasons (1998 and 1999). Surface water and soil samples were collected along an elevational gradient extending from the lightly vegetated alpine to the forested subalpine to assess how changes in land cover and basin area affect yields and concentrations of ammonium-N (NH₄-N), nitrate-N (NO₃-N), dissolved organic N (DON), and particulate organic N (PON). Streamwater yields of NO₃-N decreased downstream from 4.3 kg ha⁻¹ in the alpine to 0.75 kg ha⁻¹ at treeline, while yields of DON were much less variable (0.40–0.34 kg ha⁻¹). Yields of NH₄-N and PON were low and showed little variation with basin area. NO₃-N accounted for 40%–90% of total N along the sample transect and was the dominant form of N at all but the lowest elevation site. Concentrations of DON ranged from approximately 10% of total N in the alpine to 45% in the subalpine. For all sites, volume-weighted mean concentrations of total dissolved nitrogen (TDN) were significantly related to the DIN:DON ratio (R ² = 0.81, P < 0.001) Concentrations of NO₃-N were significantly higher at forested sites that received streamflow from the lightly vegetated alpine reaches of the catchment than in a control catchment that was entirely subalpine forest, suggesting that the alpine may subsidize downstream forested systems with inorganic N. KCl-extractable inorganic N and microbial biomass N showed no relationship to changes in soil properties and vegetative cover moving downstream in catchment. In contrast, soil carbon–nitrogen (C:N) ratios increased with increasing vegetative cover in catchment and were significantly higher in the subalpine compared to the alpine (P < 0.0001) Soil C:N ratios along the sample transect explained 78% of the variation in dissolved organic carbon (DOC) concentrations and 70% of the variation in DON concentrations. These findings suggest that DON is an important vector for N loss in high-elevation ecosystems and that streamwater losses of DON are at least partially dependent on catchment soil organic matter stoichiometry. Received 26 July 2001; accepted 6 May 2002.     

Dissolved organic nitrogen budgets for upland, forested ecosystems in New England

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 kgha^{minus 1} yr^{minus 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.     

Nutrient and mineralogical control on dissolved organic C, N and P fluxes and stoichiometry in Hawaiian soils

We measured DOM fluxes from the O horizon of Hawaiiansoils that varied in nutrient availability and mineralcontent to examine what regulates the flux ofdissolved organic carbon (DOC), nitrogen (DON) andphosphorus (DOP) from the surface layer of tropicalsoils. We examined DOM fluxes in a laboratory study from N, P and N+Pfertilized and unfertilized sites on soils that rangedin age from 300 to 4 million years old. The fluxesof DOC and DON were generally related to the % Cand % N content of the soils across the sites. Ingeneral, CO₂ and DOC fluxes were not correlatedsuggesting that physical desorption, dissolution andsorption reactions primarily control DOM release fromthese surface horizons. The one exception to thispattern was at the oldest site where there was asignificant relationship between DOC and CO₂flux. The oldest site also contained the lowestmineral and allophane content of the three sites andthe DOC-respiration correlation indicates arelationship between microbial activity and DOC fluxat this site. N Fertilization increased DON fluxes by50% and decreased DOC:DON ratios in the youngest,most N poor site. In the older, more N rich sites, Nfertilization neither increased DON fluxes nordecreased DOM C:N ratios. Similarly, short termchanges in N availability in laboratory-based soil Nand P fertilization experiments did not affect the DOMC:N ratios of leachate. DOM C:N ratios were similar tosoil organic matter C:N ratios, and changes in DOM C:Nratios with fertilization appeared to have beenmediated through long term effects on SOM C:N ratiosrather than through changes in microbial demand for Cand N. There was no relationship between DON andinorganic N flux during these incubations suggestingthat the organic and inorganic components of N fluxfrom soils are regulated by different factors and thatDON fluxes are not coupled to immediate microbialdemand for N. In contrast to the behavior of DON, thenet flux of dissolved organic phosphorus (DOP) and DOMC:P ratios responded to both long-term P fertilizationand natural variation in reactive P availability. There was lower DOP flux and higher DOM C:P ratiosfrom soils characterized by low P availability andhigh DOP flux and narrow DOM C:P ratios in sites withhigh P availability. DOP fluxes were also closelycorrelated with dissolved inorganic P fluxes. PFertilization increased DOP fluxes by 73% in theyoungest site, 31% in the P rich intermediate agesite and 444% in the old, P poor site indicating thatDOP fluxes closely track P availability in soils.     

Dissolved organic matter in small streams along a gradient from discontinuous to continuous permafrost

The Yenisei river passes every type of permafrost regime, from south to north, being characterized by increasing continuity of the permafrost and by decreasing thickness of the active layer. We used that situation to test the hypothesis that amounts and properties of dissolved organic matter (DOM) in small streams draining forested catchments respond to different permafrost regimes. Water samples were taken from eight tributaries along the Yenisei between 67°30′N and 65°49′N latitude. The samples were analysed for dissolved organic carbon (DOC) and nitrogen (DON) and DOM was characterized by its chemical composition (XAD‐8 fractionation, sugars, lignin phenols, amino acids, protein, UV and fluorescence spectroscopy), and its biodegradability. Most properties of the tributary waters varied depending on latitude. The higher the latitude, the higher were DOC, DON and the proportion of the hydrophobic fraction of DOC. The contribution of hexoses and pentoses to DOC were higher in southern tributaries; on the other hand, phenolic compounds were more abundant in northern tributaries. Mineralizable DOC ranged between 4% and 28% of total DOC. DOM in northern tributaries was significantly (P<0.05) less biodegradable than that in southern tributaries reflecting the differences in the chemical properties of DOM. Our results suggest that the differences in DOM properties are mainly attributed to differences of permafrost regime, affecting depth of active layer, soil organic matter accumulation and vegetation. Soil organic matter and vegetation determine the amount and composition of DOM produced in the catchments while the depth of the active layer likely controls the quantity and quality of DOM exported to streams. Sorptive interactions of DOM with the soil mineral phase typically increase with depth. The results imply that a northern shift of discontinuous permafrost likely will change in the long term the input of DOM into the Yenisei and thus probably into the Kara Sea.     

Factors controlling concentration, export, and decomposition of dissolved organic nutrients in the Everglades of Florida

Water draining from the Everglades marshes of southern Florida containshigh concentrations of dissolved organic C (DOC), N (DON), and in somelocations, P (DOP). These dissolved organic nutrients carry over 90% of the Nand organic C, and about 25% of the P exported downstream in the Everglades.Ourobjectives were to describe the most important aspects of the origin and fateofdissolved organic matter (DOM) in the Everglades, and to describe the processescontrolling its concentration and export. Concentrations of dissolved organicnutrients are influenced by local plant production, decomposition, and sorptionequilibrium with peat. The drained peat soils of the Everglades AgriculturalArea and the more productive marshes of the northern Everglades produce some ofthe highest concentrations of DOC and DON in the Everglades watershed. Inportions of the marshes of the northern Everglades, P enrichment was correlatedwith higher local DOC and DON concentrations and greater production of solubleplant matter. Microbial degradation of Everglades DOM was very slow; less than10% of the DOC was lost after 6 months of incubation in the laboratory andsupplements of inorganic nutrients failed to speed the decomposition. Exposureto solar radiation increased the subsequent decay rate of the remaining DOC(25%in 6 mo.). Solar radiation alone mineralized 20.5% of the DOC, 7%of the DON, and degraded about 50% of the humic substances over 21 days insterile porewater samples and thus degraded DOM faster than microbialdegradation. The humic substances appeared to inhibit biodegradation of theother fractions of the DOC since hydrophilic organic acids decomposed fasterwhen isolated from the humic substances.The fate of DOC and DON is closely linked as indicated by a generally narrowrange of C/N ratios. In contrast, high concentrations of DOP were associatedwith P enrichment (at least in pore water). The DOC was composed of about 50%humic substances, 33% hydrophilic acids, and 15% hydrophilic neutralsubstances,typical of DOC from other environments, despite the fact that it originatesfroma neutral to slightly alkaline peatland. Despite high exports of DON (3.9g m^–2 y^–1 from one area), themarshes of the northern Everglades are a sink for DON on a landscape scale. Theagricultural fields of the Everglades Agricultural Area, however, exported netquantities of DON. High concentrations of DOC desorbed from the agriculturalsoils when water with no DOC was added. Sorption experiments indicated thathighconcentrations of dissolved organic matter flowing into the marshes from theEverglades Agricultural Area could suppress the further desorption ofadditionalsoluble organic matter through physicochemical mechanisms. While biologicalfactors, plant production and microbial decomposition are important inproducingpotentially soluble organic nutrients, physicochemical sorption equilibria,hydrology, and degradation by solar radiation are also likely to control theexport of this material on the landscape scale.     

Patterns in the Chemical Fractionation of Organic Nitrogen in Rocky Mountain Streams

The intraannual dynamics of particulate organic nitrogen (PON) and two fractions of dissolved organic nitrogen (DON) were investigated in two Rocky Mountain streams draining watersheds with low rates of N deposition. Organic nitrogen accounted for over 60% of the total annual nitrogen export and consisted mostly of DON. Nitrate peaked during winter months and declined considerably during the growing season (less than 10 µg/L) suggesting the importance of biotic uptake. Concentrations of PON, total DON, and two DON fractions (humic and non-humic) peaked during spring runoff and were positively related to discharge, indicating hydrologic influence. Total DON and its two fractions showed significant inverse relationships to nitrate, indicating that DON and nitrate followed different intraannual patterns. Despite its seasonal fluctuations in concentration, PON showed a consistent carbon–nitrogen (C:N) ratio suggesting that it was relatively uniform in composition. Fractionation studies indicated that DON was primarily of non-humic origin, whereas dissolved organic carbon (DOC) was mainly derived from humic sources. The two DON fractions differed from each other in seasonal patterns of concentration and C:N ratio. The proportion of humic DON increased during snowmelt, and there were diverging seasonal patterns in the C:N ratio of the two fractions implying variations in bioavailability. Although organic nitrogen is commonly treated as a single pool in ecological studies, our results indicated that DON consists of fractions that undergo large intraannual changes in proportions and chemical composition. Treatment of DON as a single pool may be misleading from the viewpoint of understanding ecosystem processes directly related to changes in its sources and biological reactivity.     

Sources of dissolved and particulate organic material in Loch Vale Watershed,Rocky Mountain National Park,Colorado, USA

The sources of both dissolved organic carbon (DOC) and particulate organic carbon (POC) to an alpine (Sky Pond) and a subalpine lake (The Loch) in Rocky Mountain National Park were explored for four years. The importance of both autochthonous and allochthonous sources of organic matter differ, not only between alpine and subalpine locations, but also seasonally. Overall, autochthonous sources dominate the organic carbon of the alpine lake, while allochthonous sources are a more significant source of organic carbon to the subalpine lake. In the alpine lake, Sky Pond, POC makes up greater than one third of the total organic matter content of the water column, and is related to phytoplankton abundance. Dissolved organic carbon is a product of within-lake activity in Sky Pond except during spring snowmelt and early summer (May–July), when stable carbon isotope ratios suggest a terrestrial source. In the subalpine lake, The Loch, DOC is a much more important constituent of water column organic material than POC, comprising greater than 90% of the spring snowmelt organic matter, and greater than 75% of the organic matter over the rest of the year. Stable carbon isotope ratios and a very strong relation of DOC with soluble Al_(tot) indicate DOC concentrations are almost entirely related to flushing of soil water from the surrounding watershed during spring snowmelt. Stable carbon isotope ratios indicate that, for both lakes, phytoplankton is an important source of DOC in the winter, while terrestrial material of plant or microbial origin contributes DOC during snowmelt and summer.     

Degradability of dissolved soil organic carbon and nitrogen in relation to tree species

The degradability and chemical characteristics of water-extractable dissolved organic carbon (DOC) and nitrogen (DON) from the humus layer of silver birch (Betula pendula Roth), Norway spruce (Picea abies (L.) Karst.) and Scots pine (Pinus sylvestris L.) stands were compared in short-term incubation of soil solutions. For all extracts the degradation of DOC and DON was low (12-17% loss) and increased in the order: birch, spruce and pine. In the humus layer under pine a relatively larger pool of rapidly degrading dissolved soil organic matter (DOM) was indicated by the [3H]thymidine incorporation technique, which measures the availability of DOM to bacteria. The degradation of DOC was explained by a decrease in the hydrophilic fraction. For DON, however, both the hydrophilic and hydrophobic fractions tended to decrease during incubation. No major differences in concentrations of hydrophilic and hydrophobic fractions were detected between tree species. Molecular size distribution of DOC and DON, however, revealed slight initial differences between birch and conifers as well as a change in birch extract during incubation. The depletion of very rapidly degrading fractions (e.g., root exudates and compounds from the litter) may explain the low degradability of DOM in the humus layer under birch.     

Chemical Characteristics of Particulate, Colloidal, and Dissolved Organic Material in Loch Vale Watershed, Rocky Mountain National Park

The chemical relationships among particulate and colloidal organicmaterial and dissolved fulvic acid were examined in an alpine andsubalpine lake and two streams in Loch Vale Watershed, Rocky MountainNational Park. The alpine lake, Sky Pond, had the lowest dissolved organiccarbon (DOC) (0.37 mgC/L), the highest particulate carbon (POC) (0.13mgC/L), and high algal biomass. The watershed of Sky Pond is primarilytalus slope, and DOC and POC may be autochthonous. Both Andrews Creekand Icy Brook gain DOC as they flow through wet sedge meadows. Thesubalpine lake, The Loch, receives additional organic material from thesurrounding forest and had a higher DOC (0.66 mgC/L). Elemental analysis,stable carbon isotopic compositon, and ¹³C-NMR characterizationshowed that: 1) particulate material had relatively high inorganic contentsand was heterogeneous in compositon, 2) colloidal material was primarilycarbohydrate material with a low inorganic content at all sites; and 3)dissolved fulvic acid varied in compositon among sites. The lowconcentration and carbohydrate-rich character of the colloidal materialsuggests that this fraction is labile to microbial degradation and may beturning over more rapidly than particulate fractions or dissolved fulvic acid.Fulvic acid from Andrews Creek had the lowest N content and aromaticity,whereas Sky Pond fulvic acid had a higher N content and lower aromaticitythan fulvic acid from The Loch. The UV-visible spectra of the fulvic acidsdemonstrate that variation in characteristics with sources of organic carboncan explain to some extent the observed non-linear relationship betweenUV-B extinction coefficients and DOC concentrations in lakes.     

Seasonal changes in the chemical quality and biodegradability of dissolved organic matter exported from soils to streams in coastal temperate rainforest watersheds

The composition and biodegradability of streamwater dissolved organic matter (DOM) varies with source material and degree of transformation. We combined PARAFAC modeling of fluorescence excitation–emission spectroscopy and biodegradable dissolved organic carbon (BDOC) incubations to investigate seasonal changes in the lability of DOM along a soil-stream continuum in three soil types: bog, forested wetland and upland forest. The percent BDOC ranged from 7 to 38% across all sites, and was significantly greater in soil compared to streamwater in the bog and forested wetland, but not in the upland forest. The percent BDOC also varied significantly over the entire sampling period in soil and streamwater for the bog and forested wetland, as BDOC peaked during the spring runoff and was lowest during the summer months. Moreover, the chemical quality of DOM in wetland soil and streamwater was similar during the spring runoff and fall wet season, as demonstrated by the similar contribution of protein-like fluorescence (sum of tyrosine and tryptophan fluorescence) in soil water and in streams. These findings suggest that the tight coupling between terrestrial and aquatic ecosystems is responsible for the delivery of labile DOM from wetland soils to streams. The contribution of protein-like fluorescence was significantly correlated with BDOC (p < 0.001) over the entire sampling period indicating DOM is an important source of C and N for heterotrophic microbes. Taken together, our findings suggest that the production of protein-rich, labile DOM and subsequent loss in stream runoff might be an important loss of labile C and N from coastal temperate watersheds.     

Distribution of dissolved organic carbon and nitrogen in a coral reef

Dissolved organic matter (DOM) concentrations in a fringing coral reef were measured for both carbon and nitrogen with the analytical technique of high-temperature catalytic oxidation. Because of high precision of the analytical system, not only the concentrations of dissolved organic carbon and nitrogen (DOC and DON, respectively) but the C:N ratio was also determined from the distribution of DOC and DON concentrations. The observed concentrations of DOC and DON ranged 57–76 and 3.8–5.6 μmol l⁻¹, respectively. The C:N ratios of the DOM that was produced on the reef flat were very similar between seagrass- and coral-dominated areas; the C:N ratio was 10 on average. The C:N ratio of DOM was significantly higher than that of particulate organic matter (POM) that was produced on the reef flat. Production rates of DOC were measured on the reef flat during stagnant periods and accounted for 3–7% of the net primary production, depending on the sampling site. The production rate of DON was estimated to be 10–30% of the net uptake of dissolved inorganic N in the reef community. Considering that the DOM and POM concentrations were not correlated with each other, a major source of the reef-derived DOM may be the benthic community and not POM such as phytoplankton. It was concluded that a widely distributed benthic community in the coral reef released C-rich DOM to the overlying seawater, conserving N in the community.     

Land use and hydrologic flowpaths interact to affect dissolved organic matter and nitrate dynamics

The transport and transformation of dissolved organic matter (DOM) and dissolved inorganic nitrogen (DIN) through the soil profile impact down-gradient ecosystems and are increasingly recognized as important factors affecting the balance between accumulation and mineralization of subsoil organic matter. Using zero tension and tension lysimeters at three soil depths (20, 40, 60 cm) in paired forest and maize/soybean land uses, we compared dissolved organic C (DOC), dissolved organic N (DON) and DIN concentrations as well as DOM properties including hydrophilic-C (HPI-C), UV absorption (SUVA₂₅₄), humification index and C/N ratio. Soil moisture data collected at lysimeter locations suggest zero tension lysimeters sampled relatively rapid hydrologic flowpaths that included downward saturated flow through the soil matrix and/or rapid macropore flow that is not in equilibrium with bulk soil solution whereas tension lysimeters sampled relatively immobile soil matrix solution during unsaturated conditions. The effect of land use on DOC and DON concentrations was largely limited to the most shallow (20 cm) sampling depth where DOC concentrations were greater in the forest (only zero tension lysimeters) and DON concentrations were greater in the cropland (both lysimeter types). In contrast to DOC and DON concentrations, the effect of land use on DOM properties persisted to the deepest sampling depth (60 cm), suggesting that DOM in the cropland was more decomposed regardless of lysimeter type. DOC concentrations and DOM properties differed between lysimeter types only in the forest at 20 cm where soil solutions collected with zero tension lysimeters had greater DOC concentrations, greater SUVA₂₅₄, greater humification index and lower HPI-C. Our data highlight the importance of considering DOM quality in addition to DOC quantity, and indicate long-term cultivation reduced the delivery of relatively less decomposed DOM to all soil depths.     

Shining light on the storm: in-stream optics reveal hysteresis of dissolved organic matter character

The quantity and character of dissolved organic matter (DOM) can change rapidly during storm events, affecting key biogeochemical processes, carbon bioavailability, metal pollutant transport, and disinfection byproduct formation during drinking water treatment. We used in situ ultraviolet–visible spectrophotometers to concurrently measure dissolved organic carbon (DOC) concentration and spectral slope ratio, a proxy for DOM molecular weight. Measurements were made at 15-minute intervals over three years in three streams draining primarily agricultural, urban, and forested watersheds. We describe storm event dynamics by calculating hysteresis indices for DOC concentration and spectral slope ratio for 220 storms and present a novel analytical framework that can be used to interpret these metrics together. DOC concentration and spectral slope ratio differed significantly among sites, and individual storm DOM dynamics were remarkably variable at each site and among the three sites. Distinct patterns emerged for storm DOM dynamics depending on land use/land cover (LULC) of each watershed. In agricultural and forested streams, DOC concentration increased after the time of peak discharge, and spectral slope ratio dynamics indicate that this delayed flux was of relatively higher molecular weight material compared to the beginning of each storm. In contrast, DOM character during storms at the urban stream generally shifted to lower molecular weight while DOC concentration increased on the falling limb, indicating either the introduction of lower molecular weight DOM, the exhaustion of a higher molecular weight DOM sources, or a combination of these factors. We show that the combination of high-frequency DOM character and quantity metrics have the potential to provide new insight into short-timescale DOM dynamics and can reveal previously unknown effects of LULC on the chemical nature, source, and timing of DOM export during storms.

     

Atmospheric N Deposition Increases Organic N Loss from Temperate Forests

Atmospheric deposition of nitrogen (N) resulting from fossil fuel combustion has increased N inputs to temperate forests worldwide with large consequences for forest productivity and water quality. Recent work has illustrated that dissolved organic N (DON) often dominates N loss from unpolluted forests and that the relative magnitude of dissolved inorganic N (DIN) loss increases with atmospheric loading. In contrast to DIN, DON loss is thought to be controlled by soil dynamics that operate independently of N supply and demand and thus should track dissolved organic carbon (DOC) following strict stoichiometric constraints. Conversely, DON loss may shift with N supply if soil (SOM) or dissolved organic matter (DOM) is stoichiometrically altered. Here, we assess these two explanations of DON loss, which we refer to as the Passive Carbon Vehicle and the Stoichiometric Enrichment hypotheses, by analyzing patterns in soil and stream C and N in forest watersheds spanning a broad gradient in atmospheric N loading (5–45 kg N ha⁻¹ y⁻¹). We show that soil N and DON losses are not static but rather increase asymptotically with N loading whereas soil C and DOC do not, resulting in enrichment of organic N expressed as decreased soil C:N and stream DOC:DON ratios. DON losses from unpolluted sites are consistent with conservative dissolution and transport of refractory SOM. As N supply increases, however, N enrichment of organic losses is greater than expected from simple dissolution of enriched soils, suggesting activation of novel pathways of DON production or direct N enrichment of DOM. We suggest that our two hypotheses represent domains of control over forest DON loss as N supply increases but also that stoichiometric enrichment of bulk soils alone cannot fully account for large DON losses in the most N-polluted forests.     

A stormflow/baseflow comparison of dissolved organic matter concentrations and bioavailability in an Appalachian stream

Patterns of dissolved organic carbon (DOC) and nitrogen (DON) delivery were compared between times of stormflow and baseflow in Paine Run, an Appalachian stream draining a 12.4 km² forested catchment in the Shenandoah National Park (SNP), Virginia. The potential in-stream ecological impact of altered concentrations and/or chemical composition of DOM during storms also was examined, using standardized bacterial bioassays. DOC and DON concentrations in Paine Run were consistently low during baseflow and did not show a seasonal pattern. During storms however, mean DOC and DON concentrations approximately doubled, with maximum concentrations occurring on the rising limb of storm hydrographs. The rapid response of DOM concentration to changes in flow suggests a near-stream or in-stream source of DOM during storms. Stormflow (4% of the time, 36% of the annual discharge) contributed >50% of DOC, DON and NO₃ ^– flux in Paine Run during 1997. In laboratory bacterial bioassays, growth rate constants were higher on Paine Run stormflow water than on baseflow water, but the fraction of total DOM which was bioavailable was not significantly different. The fraction of the total stream DOC pool taken up by water column bacteria was estimated to increase from 0.03 ± 0.02% h^–1 during baseflow, to 0.15 ± 0.04% h^–1 during storms. This uptake rate would have a minimal effect on bulk DOM concentrations in Paine Run, but storms may still have considerable impact on the bacterial stream communities by mobilizing them into the water column and by supplying a pulse of DOM.     

马尾松与芒萁鲜叶及凋落物水溶性有机物的溶解特征和光谱学特征

为探讨福建省三明市马尾松人工林淋溶液中水溶性有机物(DOM)的溶解特征和光谱学特征,以马尾松(Pinus massoniana)和芒萁(Dicranopteris dichotoma)鲜叶、未分解层(L层)和半分解层(F层)凋落物为研究对象进行室内淋溶,对淋溶液中的水溶性有机碳(DOC)、水溶性有机氮(DON)与水溶性有机磷(DOP)含量和紫外光谱(SUVA)、荧光光谱指标和红外光谱(FTIR)等特征进行研究。结果表明,在24 h内,随着淋溶时间的延长,DOM含量呈现有波动的上升趋势;芒萁除鲜叶的DOC含量显著高于马尾松外(P0.01),其余DOM含量均小于马尾松。两植物F层DOM的SUVA值和腐殖化指标(HIX)都显著高于鲜叶和L层(P0.05),表明F层的芳香性化合物含量和腐殖化程度越来越高。DOM的同步荧光峰值显示淋溶液中含有类蛋白和类富里酸荧光团。两植物的红外光谱显示有5个相似的吸收谱带,强度最大的吸收来自于H键键合的-OH的伸缩振动,同一植物3种样品之间红外吸收的差异证明从鲜叶-L层-F层凋落物的共轭体系逐渐增大,结构更复杂。因此,随分解进程两植被DOM的化学结构越来越复杂;马尾松较芒萁含有更多的DON和DOP,这一方面为微生物提供了更多的养分,另一方面又增加了底物分解的难度。     

Bioavailability and composition of dissolved organic carbon and nitrogen in a near coastal catchment of south-western Australia

The bioavailability and composition of dissolved organic carbon (DOC) and nitrogen (DON) were examined in 10 major sub-catchments of the Swan-Canning estuary, which bisects the city of Perth, in south-western Australia. Catchments contain a mix of forest, agriculture, and urban-dominated land-use, with the degree of development increasing near the city center. We incubated water samples from the 10 sub-catchments for 14 days at 25°C, and measured changes in DOC and DON and dissolved inorganic nitrogen (DIN). A greater proportion of DON (4–44%) was decomposed compared to DOC (1–17%). Both agricultural and urban catchments had high proportions of bioavailable DOC and DON, but overall DOC and DON losses were greatest in urban catchments. Using resin isolation techniques, we found that DOC was concentrated in the hydrophobic (humic) fraction, whereas DON had both hydrophobic and hydrophilic (non-humic) fractions. Hydrophobic DOC content was positively related to DOC decomposition. In contrast, DON decomposition was highly correlated with hydrophilic DON content and inversely related to the hydrophilic DOC/DON ratio, indicating a labile fraction of DON from non-humic sources. Taken together, these relationships suggest that bioavailable DOC may be supplied in part from terrestrial plant material, but bioavailable DON is likely to be from highly labile sources, possibly autochthonous or anthropogenic. Overall, labile DON was greater than initial DIN concentration at seven of ten sites and was even dominant in highly developed catchments. This study highlights the importance of organic N in urbanizing coastal catchments that, in addition to DIN, may serve as a readily available source of N for in-stream and estuarine production.     

Shifting stoichiometry: Long-term trends in stream-dissolved organic matter reveal altered C:N ratios due to history of atmospheric acid deposition

Dissolved organic carbon (DOC) and nitrogen (DON) are important energy and nutrient sources for aquatic ecosystems. In many northern temperate, freshwater systems DOC has increased in the past 50 years. Less is known about how changes in DOC may vary across latitudes, and whether changes in DON track those of DOC. Here, we present long-term DOC and DON data from 74 streams distributed across seven sites in biomes ranging from the tropics to northern boreal forests with varying histories of atmospheric acid deposition. For each stream, we examined the temporal trends of DOC and DON concentrations and DOC:DON molar ratios. While some sites displayed consistent positive or negative trends in stream DOC and DON concentrations, changes in direction or magnitude were inconsistent at regional or local scales. DON trends did not always track those of DOC, though DOC:DON ratios increased over time for ~30% of streams. Our results indicate that the dissolved organic matter (DOM) pool is experiencing fundamental changes due to the recovery from atmospheric acid deposition. Changes in DOC:DON stoichiometry point to a shifting energy-nutrient balance in many aquatic ecosystems. Sustained changes in the character of DOM can have major implications for stream metabolism, biogeochemical processes, food webs, and drinking water quality (including disinfection by-products). Understanding regional and global variation in DOC and DON concentrations is important for developing realistic models and watershed management protocols to effectively target mitigation efforts aimed at bringing DOM flux and nutrient enrichment under control.