Fate and Transport of Organic Nitrogen in Minimally Disturbed Montane Streams of Colorado,USA

In two montane watersheds that receive minimal deposition of atmospheric nitrogen, 15–71% of dissolved organic nitrogen (DON) was bioavailable in stream water over a 2-year period. Discharge-weighted concentrations of bulk DON were between 102 and 135 μg/l, and the C:N ratio differed substantially between humic and non-humic fractions of DON. Approximately 70% of DON export occurred during snowmelt, and 40% of that DON was biologically available to microbes in stream sediments. Concentrations of bioavailable DON in stream water were 2–16 times greater than dissolved inorganic nitrogen (DIN) during the growing season, and bioavailable DON was depleted within 2–14 days during experimental incubations. Uptake of DON was influenced by the concentration of inorganic N in stream water, the concentration of non-humic DON in stream water, and the C:N ratio of the non-humic fraction of dissolved organic matter (DOM). Uptake of DON declined logarithmically as the concentration of inorganic N in stream water increased. Experimental additions of inorganic N also caused a decline in uptake of DON and net production of DON when the C:N ratio of non-humic DOM was high. This study indicates that the relative and absolute amount of bioavailable DON can vary greatly within and across years due to interactions between the availability of inorganic nutrients and composition of DOM. DOM has the potential to be used biotically at a high rate in nitrogen-poor streams, and it may be generated by heterotrophic microbes when DIN and labile DOM with low relative nitrogen content become abundant.     

杉木人工林土壤可溶性有机质及其与土壤养分的关系

通过在福建省来舟林场对不同栽植代数杉木人工林土壤可溶性有机碳(DOC)和氮(DON)及土壤养分的研究,其结果表明,随着杉木栽植代数的增加林地土壤DOC和DON含量逐渐下降,在0～10cm土层内第3代杉木林土壤DOC和DON含量分别是第1代杉木林的83.9%和87.1%、第2代杉木林的90.6%和96.9%,在10～20cm土层内第3代杉木林土壤DOC和DON含量分别是第1代杉木林的80.2%和81.5%、第2代杉木林的81.8%和90.0%。在不同林地和土层内土壤DOC含量之间的差异性达到了显著或极显著水平,而DON含量之间的差异性不显著。不同栽植代数杉木林土壤养分的变化趋势与DOM一致,随着杉木连栽,土壤养分含量呈下降趋势。在0～10cm土层内第3代杉木林土壤全氮、全钾、铵态氮和速效钾含量分别是第1代杉木林的83.1%、60.4%、68.1%和44.3%,是第2代杉木林的84.6%、68.5%、74.4%和58.7%;在10～20cm土层内第3代杉木林土壤全氮、全钾、铵态氮和速效钾含量分别是第1代杉木林的74.0%、53.4%、57.6%和54.6%,是第2代杉木林的94.8%、59.5%、74.3%和65.5%。经相关性分析,在各土层内土壤DOC和DON含量与土壤全氮、全钾、铵态氮和速效钾等土壤养分含量存在着不同程度的相关性。     

Hydrologic Drivers and Seasonality of Dissolved Organic Carbon Concentration, Nitrogen Content, Bioavailability, and Export in a Forested New England Stream

We present the results of a full year of high-resolution monitoring of hydrologic event-driven export of stream dissolved organic matter (DOM) from the forested Bigelow Brook watershed in Harvard Forest, Massachusetts, USA. A combination of in situ fluorescent dissolved organic matter (FDOM) measurement, grab samples, and bioassays was utilized. FDOM was identified as a strong indicator of concentration for dissolved organic carbon (DOC, r ² = 0.96), dissolved organic nitrogen (DON, r ² = 0.81), and bioavailable DOC (BDOC, r ² = 0.81). Relationships between FDOM and concentration were utilized to improve characterization of patterns of hydrological event-driven export and the quantification of annual export. This characterization was possible because DOM composition remained relatively consistent seasonally; however, a subtle shift to increased fluorescence per unit absorbance was observed for summer and fall seasons and percent BDOC did increase slightly with increasing concentrations. The majority of export occurred during pulsed hydrological events, so the greatest impact of bioavailable exports may be on downstream aquatic ecosystems. Export from individual events was highly seasonal in nature with the highest flow weighted mean concentrations (DOC_FW) being observed in late summer and fall months, but the highest total export being observed for larger winter storms. Seasonal trends in DOC export coincide with weather driven changes in surface and subsurface flow paths, potential for depletion and rebuilding of a flushable soil organic matter pool, and the availability of terrestrial carbon sources such as leaf litter. Our approach and findings demonstrate the utility of high frequency FDOM measurement to improve estimates of intra-annual temporal trends of DOM export.     

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。     

Irrigation as a fuel pump to freshwater ecosystems

We generated a detailed time series of total dissolved hydrolyzable amino acids (DHAA) in a watershed dominated by irrigated agriculture in northern California, USA to investigate the roles of hydrologic and seasonal changes on the composition of dissolved organic matter (DOM). DHAA are sensitive indicators of the degradation state and reactivity of DOM. DHAA concentrations ranged from 0.55 to 9.96 μM (median 3.51 ± 1.80 μM), with expected peaks during high-discharge storms and unexpected high values throughout the low-discharge irrigation season. Overall, summer irrigation was a critical hydrologic regime for DOM cycling since it mobilized DOM similar in concentration and reactivity to DOM released during storms. Together, irrigation and storm flows exported DOM with (1) the largest DHAA contributions to the dissolved organic carbon and the dissolved organic nitrogen pools, (2) the largest proportion of basic amino acids, and (3) the lowest degradation extent based on multiple indices. In this highly disturbed terrestrial system, UV–vis absorbance did not correlate with DHAA concentrations, while classic interpretations of common amino acid indicators (e.g., proportion of basic amino acids, degradation index, percent of non-protein amino acids) were prone to conflicting characterizations of DOM reactivity. Therefore, a new parameter (processing ratio, PR) derived from individual amino acid concentrations was developed that demonstrated a strong potential for mechanistic-driven characterization of the extent of DOM diagenesis in freshwaters. Irrigated agriculture altered stream biogeochemistry by releasing a continuous supply of reactive DOM (lowest PR values), thereby providing an additional energy source to downstream ecosystems.     

Seasonal variability of inorganic and organic nitrogen in the North Sea

This study considers the cycling of nitrogen in the waters of the North Sea, particularly focussing on organic nitrogen. Dissolved inorganic nitrogen (DIN), dissolved organic nitrogen (DON) and particulate organic nitrogen (PON) were measured in the North Sea over a one-year period (autumn 2004–summer 2005). The surface water concentrations of nitrate, ammonium, DON and PON during the present study ranged from <0.1–7.2 μM, <0.1–2.0 μM, 1.9–11.2 μM and 0.3–5.6 μM, respectively, with DON the dominant fraction of total nitrogen at all times. These nutrients concentrations were significantly lower compared to previous studies in the southern North Sea. The seasonal variations showed high mean surface concentrations of nitrate (4.7 ± 0.6 μM) and DON (8.9 ± 0.9 μM), low ammonium (<0.1 μM) and PON (0.8 ± 0.1 μM) in winter, shifting to low nitrate (0.3 ± 0.3 μM) and DON (4.2 ± 1.2 μM) in summer, with high ammonium (0.8 ± 0.4 μM) in autumn and PON (2.5 ± 1.2 μM) in spring. Highest mean surface DON concentration was measured in winter and may be due to resuspension of the organic matter from the bottom sediments. For autumn and spring, phytoplankton DON release was likely to be the most significant source of DON as shown by high concentrations of low molecular weight (LMW) DON and its positive correlation to chlorophyll a. Low total and LMW DON concentrations during summer were likely to be due to the uptake of the LMW DON fraction by phytoplankton and bacteria and the stratification of the water column. DON is therefore shown to be a potentially important source of nitrogen in shelf seas especially after the spring bloom has depleted nitrate to limiting concentrations. Handling editor: L. Naselli-Flores     

Interannual variability of Aureococcus anophagefferens in Quantuck Bay, Long Island: natural test of the DON hypothesis

This study examined benthic and pelagic rate processes from the perspective of benthic dissolved organic matter (DOM) and its possible role in Aureococcus anophagefferens population dynamics. Sampling was conducted in Quantuck Bay, Long Island, New York, at three times in the summer of 2000 and two times in the summer of 2001. A. anophagefferens exhibited a large bloom between the May and July 2000 sample periods, but a smaller bloom was captured in the September 2000 sampling. Densities throughout 2001 were significantly lower than during 2000. There were few differences in most parameters measured between years, but the largest difference was the seasonal increase in both particulate (POM) and dissolved organic matter (DOM) during 2000 that was not observed during 2001. In particular, DOP accumulated the most, followed by DON and DOC, which resulted in significant seasonal decreases in the C:N:P ratios of the DOM pools. On the contrary, changes in elemental ratios of POM were not observed. The seasonal accumulation of DON appeared to be driven largely (50%) by the flux of DON from the benthos in 2000, but during 2001, all measured DON fluxes were into the sediment from the water column. This is consistent with the lack of accumulation during this year. There was little evidence for changes in microzooplankton grazing pressure between 2000 and 2001, and therefore the accumulation of DON and DOP during 2000 could have provided a competitive advantage to A. anophagefferens over other picoalgal species (e.g., Synechococcus) resulting in the significant blooms observed in 2000.     

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.     

Bioavailability and size-fraction of dissolved organic carbon, nitrogen, and sulfur at the Arbutus Lake watershed, Adirondack Mountains, NY

The heterogeneity of DOM is closely linked with the various sources and the diversity of biogeochemical processes. We studied the spatial and temporal patterns of the quantity (bioavailable [B-] and refractory concentrations by laboratory incubations) and quality (δ¹³C, aromaticity, and size-fraction by ultrafiltration [low molecular weight (LMW) < 1 kDa and high molecular weight (HMW) > 1 kDa]) of dissolved organic C (DOC), N (DON), and S (DOS) for surface waters (two upland streams, two wetland-affected streams, and lake outlet) over a 14-month period within the Arbutus Lake watershed in the Adirondack Mountains of New York State, USA. The % BDOC and % BDON of this watershed averages ranged from 6 to 18 % and from 12 to 43 %, respectively. The DOC and DON concentrations increased as water was transported through wetland areas of the Arbutus Lake watershed. DOC and DON constituents in the surface waters passing through a wetland were composed mostly of refractory HMW components (% HMWDOC: 55 %, % HMWDON: 60 %) with a higher level of aromaticity compared to upland streams (% HMWDOC: approximately 35 %, % HMWDON: approximately 30 %). DOS was dominated by the refractory (% BDOS range 6–13 %) and LMW (% LMWDOS range 62–96 %) form and we suggest that bacterial dissimilatory sulfate reduction might play an important role in generating this distinct DOS biogeochemistry. The aromaticity was positively related to total DOC concentration, but negatively to % BDOC. Arbutus Lake DOM was dominated by bioavailable and LMW characteristics, compared to wetland-affected streams where refractory and HMW DOM fractions were more prevalent. Our study suggests the different variability of DOM characteristics among elements (C, N, S) using a “bioavailability-molecular size model” showing a diagenetic perspective due to the relative refractoriness of the LMW DOS. This study also highlights the importance of multiple approaches for understanding DOM biogeochemistry with respect to molecular size, bioavailability, aromaticity, stoichiometry, isotopic values, and elemental concentrations.     

Origin and fate of dissolved organic matter in four shallow Baltic Sea estuaries

Coastal waters have strong gradients in dissolved organic matter (DOM) quantity and characteristics, originating from terrestrial inputs and autochthonous production. Enclosed seas with high freshwater input therefore experience high DOM concentrations and gradients from freshwater sources to more saline waters. The brackish Baltic Sea experiences such salinity gradients from east to west and from river mouths to the open sea. Furthermore, the catchment areas of the Baltic Sea are very diverse and vary from sparsely populated northern areas to densely populated southern zones. Coastal systems vary from enclosed or open bays, estuaries, fjords, archipelagos and lagoons where the residence time of DOM at these sites varies and may control the extent to which organic matter is biologically, chemically or physically modified or simply diluted with transport off-shore. Data of DOM with simultaneous measurements of dissolved organic (DO) nitrogen (N), carbon (C) and phosphorus (P) across a range of contrasting coastal systems are scarce. Here we present data from the Roskilde Fjord, Vistula and Öre estuaries and Curonian Lagoon; four coastal systems with large differences in salinity, nutrient concentrations, freshwater inflow and catchment characteristics. The C:N:P ratios of DOM of our data, despite high variability, show site specific significant differences resulting largely from differences residence time. Microbial processes seemed to have minor effects, and only in spring did uptake of DON in the Vistula and Öre estuaries take place and not at the other sites or seasons. Resuspension from sediments impacts bottom waters and the entire shallow water column in the Curonian Lagoon. Finally, our data combined with published data show that land use in the catchments seems to impact the DOC:DON and DOC:DOP ratios of the tributaries most.

     

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.     

Retention of soluble organic nutrients by a forested ecosystem

We document an example of a forested watershed at the Coweeta HydrologicLaboratory with an extraordinary tendency to retain dissolved organic matter(DOM) generated in large quantities within the ecosystem. Our objectives weretodetermine fluxes of dissolved organic C, N, and P (DOC, DON, DOP,respectively),in water draining through each stratum of the ecosystem and synthesizeinformation on the physicochemical, biological and hydrologic factors leadingtoretention of dissolved organic nutrients in this ecosystem. The ecosystemretained 99.3, 97.3, and 99.0% of water soluble organic C, N and P,respectively, produced in litterfall, throughfall, and root exudates. Exportsinstreamwater were 4.1 kg ha^–1yr^–1of DOC, 0.191 kg ha^–1 yr^–1 ofDON, and 0.011 kg ha^–1 yr^–1 ofDOP. Fluxes of DON were greater than those of inorganic N in all strata. MostDOC, DON, and DOP was removed from solution in the A and B horizons, with DOCbeing rapidly adsorbed to Fe and Al oxyhydroxides, most likely by ligandexchange. DON and DOC were released gradually from the forest floor over theyear. Water soluble organic C produced in litterfall and throughfall had adisjoint distribution of half-decay times with very labile and veryrefractory fractions so that most labile DOC was decomposed before beingleachedinto the mineral soil and refractory fractions dominated the DOC transportedthrough the ecosystem. We hypothesize that this watershed retained solubleorganic nutrients to an extraordinary degree because the soils have very highcontents of Fe and Al oxyhydroxides with high adsorption capacities and becausethe predominant hydrologic pathway is downwards as unsaturated flow through astrongly adsorbing A and B horizon. The well recognized retention mechanismsforinorganic nutrients combine with adsorption of DOM and hydrologic pathway toefficiently prevent leaching of both soluble inorganic andorganic nutrients in this watershed.     

Dissolved organic matter (DOM) concentration and quality in a forested mid-Atlantic watershed, USA

Understanding the quantity and quality of dissolved organic matter (DOM) in potential watershed sources is critical for explaining and quantifying the exports of DOM in stream runoff. Here, we examined the concentration and quality of DOM for ten watershed sources in a 12?ha forested catchment over a two-year period. DOM composition was evaluated for: throughfall, litter leachate, soil water (zero and tension), shallow and deep groundwater, stream water, hyporheic zone, and groundwater seeps. DOM quality was measured using a suite of optical indices including UV–visible absorbance and PARAFAC modeling of fluorescence excitation-emission matrices (EEMs). DOM concentrations and quality displayed a pronounced trend across watershed sources. Surficial watershed sources had higher DOM concentrations and more humic-like DOM with higher molecular weight whereas deeper groundwater sources were rich in % protein-like fluorescence. The greater % contribution of protein-like fluorescence in groundwater suggested that a larger fraction of groundwater DOM may be bioavailable. DOM for wetland groundwater was more aromatic and humic-like than that at the well-drained riparian location. Principal component analyses (PCA) revealed that the differences in surficial watershed compartments were dictated by humic-like components while groundwater sources separated out by % protein-like fluorescence. Observations from optical indices did not provide any conclusive evidence for preferential association of dissolved organic carbon (DOC) or dissolved organic nitrogen (DON) with any particular DOM quality pools.     

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.     

Controls on the release of dissolved organic carbon and nitrogen from a deciduous forest floor investigated by manipulations of aboveground litter inputs and water flux

Although dissolved organic matter (DOM) released from the forest floor plays a crucial role in transporting carbon and major nutrients through the soil profile, its formation and responses to changing litter inputs are only partially understood. To gain insights into the controlling mechanisms of DOM release from the forest floor, we investigated responses of the concentrations and fluxes of dissolved organic carbon (DOC) and nitrogen (DON) in forest floor leachates to manipulations of throughfall (TF) flow and aboveground litter inputs (litter removal, litter addition, and glucose addition) at a hardwood stand in Bavaria, Germany. Over the two-year study period, litter manipulations resulted in significant changes in C and N stocks of the uppermost organic horizon (Oi). DOC and DON losses via forest floor leaching represented 8 and 11% of annual litterfall C and N inputs at the control, respectively. The exclusion of aboveground litter inputs caused a slight decrease in DOC release from the Oi horizon but no change in the overall leaching losses of DOC and DON in forest floor leachates. In contrast, the addition of litter or glucose increased the release of DOC and DON either from the Oi or from the lower horizons (Oe + Oa). Net releases of DOC from the Oe + Oa horizons over the entire manipulation period were not related to changes in microbial activity (measured as rates of basal and substrate-induced respiration) but to the original forest floor depths prior to manipulation, pointing to the flux control by the size of source pools rather than a straightforward relationship between microbial activity and DOM production. In response to doubled TF fluxes, net increases in DOM fluxes occurred in the lower forest floor, indicating the presence of substantial pools of potentially soluble organic matter in the Oe + Oa horizons. In contrast to the general assumption of DOM as a leaching product from recent litter, our results suggest that DOM in forest floor leachates is derived from both newly added litter and older organic horizons through complex interactions between microbial production and consumption and hydrologic transport.     

Heterogeneous dissolved organic nitrogen supply over a coral reef: first evidence from nitrogen stable isotope ratios

Dissolved organic nitrogen (DON) potentially plays a major role in sustaining the high productivity and biological diversity of coral reefs. However, data are scarce regarding sources and sinks of DON. This study, for the first time, determined the ¹⁵N isotopic composition of total dissolved nitrogen (δ¹⁵N_TDN), reflecting the isotopic signature of DON, in the water column over a coral reef. The uniformity in δ¹⁵N_TDN during high tide (3.2 ± 0.3 ‰) indicated that the DON was mainly derived from offshore waters. In contrast, higher spatial heterogeneity of δ¹⁵N_TDN (3.1 ± 0.9 ‰) and DON concentrations during low tide indicated the existence of local DON sources patchily distributed over the reef. Low δ¹⁵N_TDN values located mid-reef were indicative of DON release from organisms that obtained their N via N₂ fixation, whereas high δ¹⁵N_TDN appeared to reflect localized release of DON by organisms exposed to dissolved inorganic nitrogen with elevated ¹⁵N, such as from terrestrial and offshore inputs. Collectively, the results highlight the importance of spatial patterns in DON release from reef communities in the N cycling of coral reefs.     

Characterising the seasonal cycle of dissolved organic nitrogen using Cefas SmartBuoy high-resolution time-series samples from the southern North Sea

The Cefas SmartBuoy network provides a unique insight into the biogeochemical dynamics of the Northern European shelf seas, particularly the North Sea, through high-resolution automated offshore water sampling. We present total dissolved nitrogen and dissolved organic nitrogen (DON) from the Dowsing SmartBuoy site (53.531° N, 1.053° E) from January to October 2010, the first high resolution seasonal (winter-autumn) cycle of DON from the open North Sea. On top of a refractory background DON concentration of approximately 5 μM, a rapid increase in DON of a further ～5 μM is observed over the course of the spring bloom. This rapidly produced DON declines at an estimated net decay rate of between 0.6 and 1.8 μM month^?1. The slow decay suggests that the majority of the additional DON produced during the spring bloom is of semi-labile nature and has a lifetime of weeks to months. The dataset allows us to tightly constrain the budget for water column nitrogen over the winter, spring and summer of 2010 and clearly demonstrates the ‘sawtooth’ nature of the seasonal cycle of DON in the open North Sea, which has been impossible to resolve with a more traditional ship-based mode of operation. This work highlights the importance of autonomous sampling approaches in better understanding shelf sea biogeochemistry in the future.     

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.     

Potential effects of leaf litter on water quality in urban watersheds

Leaf litter plays a critical role in regulating ecological functions in headwater forest streams, whereas the effects of leaves on water quality in urbanized streams are not fully understood. This study examined the potential importance of leaf litter for the release and transformations of organic carbon and nutrients in urban streams, and compared the effects with other types of natural organic substrates (periphyton and stream sediment). Nutrients and organic carbon were leached from senescent leaves of 6 tree species in the laboratory with deionized water, and maximal releases, leaching rate constants, composition and bioavailability of the leached dissolved organic carbon (DOC) were determined. Stream substrates (leaf debris, rocks with periphyton, and sediment) were seasonally collected from urban and forest reference streams of the NSF Baltimore Long-term Ecological Research Site and incubated with overlying stream water to estimate areal fluxes of DOC and nitrogen. Leaf litter leaching showed large ranges in maximal releases of DOC (7.0–131 mg g^?1), dissolved organic nitrogen (DON; 0.07–1.39 mg g^?1) and total dissolved phosphorus (TDP; 0.14–0.70 mg g^?1) among tree species. DOC leaching rate constants, carbon to nitrogen ratios, and DOC bioavailability were all correlated with organic matter quality indicated by fluorescence spectroscopy. Results from substrate incubation experiments showed far higher DOC and DON release and nitrate retention with leaf debris than with sediment, or rocks with periphyton. DOC release from leaf debris was positively correlated with stream nitrate retention at residential and urban sites, with the highest values observed during the fall and lowest during the summer. This study suggests the potential importance of leaf litter quantity and quality on fostering DOC and nutrient release and transformations in urban streams. It also suggests that species-specific impacts of leaves should be considered in riparian buffer and stream restoration strategies.