Seasonal and spatial variability of dissolved organic matter composition in the lower Amazon River

We analyzed the molecular composition of dissolved organic matter (DOM) in the lower Amazon River (ca. 850 km from Óbidos to the mouth) using ultrahigh-resolution mass spectrometry and geochemical tracers. Changes in DOM composition along this lower reach suggest a transition from higher plant-derived DOM to more algal/microbial-derived DOM. This result was likely due to a combination of autochthonous production, alteration of terrigenous DOM as it transits down the river, and increased algal inputs from floodplain lakes and clearwater tributaries during high discharge conditions. Spatial gradients in dissolved organic carbon (DOC) concentrations varied with discharge. Maximal DOC concentrations were observed near the mouth during high water, highlighting the importance of lateral inputs of DOM along the lower river. The majority of DOM molecular formulae did not change within the time it takes the water in the mainstem to be transported through the lower reach. This is indicative of molecules representing a mixture of compounds that are resistant to rapid alteration and reactive compounds that are continuously replenished by the lateral input of terrestrial organic matter from the landscape, tributaries, and floodplains. River water incubations revealed that photo- and bio-transformation alter at most 30% of the DOM molecular formulae. River discharge at the mouth differed from the sum of discharge measurements made at Óbidos and the main gauged tributaries in the lower Amazon. This indicates that changes in hydrology and associated variations in the source waters along the lower reach affected the molecular composition of the DOM that is being transported from the Amazon River to the coastal ocean.     

Colloidal and dissolved organic matter in lake water: Carbohydrate and amino acid composition,and ability to support bacterial growth

Bacterial utilization of dissolved organic matter (DOM) was studied in water from a humic and a clearwater oligotrophic lake. Indigenous bacteria were inoculated into either 0.2 m natural filtered lake water, or lake water enriched fivefold with colloidal DOM >100 kD but below 0.2 m. Consumption of DOM was followed from changes in concentrations of total dissolved organic carbon (DOC), dissolved combined and free carbohydrates and amino acids (DCCHO and DFCHO, and DCAA and DFAA, respectively) and by uptake of monosaccharide and amino acid radioisotopes. DCCHO and DCAA made up 8% (humic lake) to 33–44% (clear-water lake) of the natural DOC pools, while DFCHO and DFAA contributed at most 1.7% to the DOC pools. Addition of >100 kD DOM increased the DOC concentrations by 50% (clearwater lake) to 92% (humic lake), but it only resulted in a higher bacterial production (by 63%) in the humic lake. During the incubations 13 to 37% of the DOC was assimilated by the bacteria, at estimated growth efficiencies of 4–8%. Despite the measured reduction of DOC, statistically significant changes of specific organic compounds, especially of DCCHO and DCAA, generally did not occur. Probably the presence of high molecular weight DOC interfered with the applied analytical procedures. Addition of radiotracers indicated, however, that DFAA sustained 17–58% and 29–100% of the bacterial carbon and nitrogen requirements, respectively, and that glucose met 1–3% of the bacterial carbon requirements. Thus, our experiments indicate that radiotracers, rather than measurements of concentration changes, should be used in studies of bacterial utilization of DOC in freshwaters with a high content of humic or high molecular weight organic matter.     

Small scale variability of vertical water and dissolved organic matter fluxes in sandy Cambisol subsoils as revealed by segmented suction plates

Dissolved organic matter (DOM) is considered as a major carbon source in subsoils. As soil water fluxes are highly variable at small scale, and transport versus sorptive retention of DOM is related to water flux and associated contact time with minerals, knowledge of the small scale spatial variability of the dissolved organic carbon (DOC) concentrations and fluxes into the subsoil is decisive for a solid estimation of organic carbon (OC) translocation into the subsoil. Here, we made advantage of novel segmented suction plates (4 × 4 segments, each 36 cm²) to analyze the small scale spatial and temporal variability of DOC transport at 10, 50 and 150 cm depth of three subsoil observatories (approximately 50 m apart) in a sandy Dystric Cambisol under beech in the Grinderwald, 40 km northwest from Hannover, Germany. Water fluxes, DOC concentrations and fluxes as well as the specific UV absorbance (SUVA) at 280 nm were determined in weekly samples from August 2014 to November 2015 for each individual segment. The DOC fluxes decreased with depth (19.6 g C m^?2 year^?1, 10 cm; 1.2 g C m^?2 year^?1, 150 cm) and were strongly related to the water fluxes. The SUVA at 280 nm also decreased with depth (0.03 L mg C^?1 cm^?1, 10 cm; 0.01 L mg C^?1 cm^?1, 150 cm), indicating a selective retention of aromatic moieties, that was eased with increasing water flux at least in the subsoil. The proportion of temporal fluctuations and small scale variability on the total variance of each parameter where determined by the calculation of intra class correlations. The seasonal heterogeneity and the small scale spatial heterogeneity were identified to be of major importance. The importance of the small scale spatial heterogeneity strongly increased with depth, pointing towards the stability of flow paths and suggesting that at a given substrate hydrological processes rather than physicochemical processes are decisive for the sorptive retention of DOM and the variability of OC accumulation in the subsoil. Our results clearly show the demand of small scale sampling for the identification of processes regarding carbon cycling in the subsoil.     

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.     

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.     

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.     

Sources and ages of dissolved organic matter in peatland streams: evidence from chemistry mixture modelling and radiocarbon data

Monitoring data over the period 1994–2007 were analysed for three streams (Cottage Hill Sike, CHS; Rough Sike, RS; Trout Beck, TB) draining blanket peat underlain by glacial clay and limestone-rich sub-strata at Moor House (Northern England). Dissolved organic carbon concentration, [DOC], showed complex relationships with both discharge and calcium concentration, [Ca]. A model based on [Ca] was constructed to simulate stream [DOC] by mixing dissolved organic matter (DOM) from shallow peat, quantified by measured [DOC] (15–30 mg l^?1) in peat porewater, with DOM assumed to be present at a constant concentration (c. 5 mg l^?1) in groundwater. A temperature-based adjustment to the measured porewater [DOC] was required to account for relatively low streamwater [DOC] during winter and spring. The fitted model reproduced short-term variation in streamwater [DOC] satisfactorily, in particular variability in RS and TB due to groundwater contributions. Streamwater DOM is largely derived from surface peat, which accounts for more than 96% of the total DOC flux in both RS and TB, and 100% in CHS. Model outputs were combined with streamwater and porewater DO¹⁴C data to estimate the ¹⁴C contents, and thereby the ages, of DOM from peat and groundwater. The peat-derived DOM is 5 years old on average, with most of it very recently formed. The derived age of groundwater DOM (8,500 years) is comparable to the 4,000–7,000 years estimated from the DO¹⁴C of water extracts of clay underlying the peat, suggesting that the clay is the source of groundwater DOM.     

Biogeochemical processes in the groundwater discharge zone of urban streams

The influence of biogeochemical processes on nitrogen and organic matter transformation and transport was investigated for two urban streams receiving groundwater discharge during the dry summer baseflow period. A multiple lines of evidence approach involving catchment-, and stream reach-scale investigations were undertaken to describe the factors that influence pore water biogeochemical processes. At the catchment-scale gaining stream reaches were identified from water table mapping and groundwater discharge estimated to be between 0.1 and 0.8 m³ m^?2 d^?1 from baseflow analysis. Sediment temperature profiles also suggested that the high groundwater discharge limited stream water infiltration into the sediments. At the stream reach-scale, dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations were higher in stream water than in groundwater. However, DOC and DON concentrations were greatest in sediment pore water. This suggests that biodegradation of sediment organic matter contributes dissolved organic matter (DOM) to the streams along with that delivered with groundwater flow. Pore water ammonium (NH₄ ⁺) was closely associated with areas of high pore water DOM concentrations and evidence of sulfate (SO₄ ^2?) reduction (low concentration and SO₄:Cl ratio). This indicates that anoxic DOM mineralization was occurring associated with SO₄ ^2? reduction. However the distribution of anoxic mineralization was limited to the center of the streambed, and was not constrained by the distribution of sediment organic matter which was higher along the banks. Lower sediment temperatures measured along the banks compared to the center suggests, at least qualitatively, that groundwater discharge is higher along the banks. Based on this evidence anoxic mineralization is influenced by groundwater residence time, and is only measurable along the center of the stream where groundwater flux rates are lower. This study therefore shows that the distribution of biogeochemical processes in stream sediments, such as anoxic mineralization, is strongly influenced by both the biogeochemical conditions and pore water residence time.     

Instream release of dissolved organic matter from coarse and fine particulate organic matter of different origins

Dissolved organic matter (DOM), produced through leaching from particulate organic matter (POM), is an essential component of the carbon cycle in streams. The present study investigated the instream DOM release from POM, varying in size and chemical quality. We produced large and medium sized fine particulate organic matter (L-FPOM, 250–500 μm; M-FPOM, 100–250 μm) of defined quality by feeding five types of coarse particulate organic matter (CPOM) to shredding amphipods (Gammarus spp.). Microscopic observations showed that L-FPOM and M-FPOM mainly consisted of the fecal pellets of amphipods, and incompletely eaten plant fragments, respectively. DOM release experiments were conducted by exposing CPOM and M- and L-FPOM fractions in natural stream water over a two week period. For CPOM, the release of dissolved organic carbon (DOC) by leaching was highest during the first 6 h (3.64–23.9 mg C g C^?1 h^?1) and decreased rapidly afterwards. For M- and L-FPOM, the DOC release remained low during the entire study period (range: 0.008–0.15 mg C g C^?1 h^?1). Two-way ANOVA revealed that the DOC release rate significantly differed with POM source and size fraction, both at day 1 and after a week of exposure. Multiple regression analyses revealed a significant correlation of elemental contents and lignin content to DOC release rate after a week of exposure. Overall, the results indicated that DOC release rate of FPOM, on a carbon basis, is comparable to that of CPOM after leaching, while size and source of POM significantly affect DOC release rate.     

Influence of soil temperature and moisture on the dissolved carbon,nitrogen, and phosphorus in organic matter entering lake ecosystems

Concentrations of terrestrially derived dissolved organic matter (DOM) have been increasing in many north temperate and boreal lakes for over two decades. The concentration of DOM in lakes is influenced by a number of environmental factors, but there is still considerable debate about how the availability of terrestrial DOM, and associated dissolved nitrogen and phosphorus, may be affected by drivers of climatic change. Using experimental and observational methods, we considered how changes in soil temperature and moisture affected the composition of carbon, nitrogen, and phosphorus entering freshwater lakes. In our experiment, organic soil cores were collected from the wetland shoreline of a darkly-stained seepage lake in northern Wisconsin, USA and manipulated in laboratory with temperature and moisture treatments. During the 28-day study, soil leachate was sampled and analyzed for optical properties of DOM via UV/Vis absorbance, as well as concentrations of dissolved organic carbon (DOC), total dissolved nitrogen, and total dissolved phosphorus (TDP). DOM optical properties were particularly sensitive to moisture, with drier scenarios resulting in DOM of lower molecular weight and aromaticity. Warmer temperatures led to lower DOC and TDP concentrations. To consider long-term relationships between climate and lake chemical properties, we analyzed long-term water chemistry data from two additional Wisconsin lakes from the long term ecological research (LTER) project in a cross correlation analysis with Palmer drought severity index data. Analysis of the LTER data supported our experimental results that soil moisture has a significant effect on the quality of DOM entering lakes and that climate may significantly affect lake chemical properties. Although unexpected in terms of DOM loading for climate change scenarios, these results are consistent with patterns of decomposition in organic soils and may be attributed to an increase in soil DOM processing.     

Sustained Biogeochemical Impacts of Wildfire in a Mountain Lake Catchment

Wild and prescribed fires can cause severe deterioration in water quality, including increases in sediment, nutrients and dissolved organic carbon (DOC). Due to the unpredictability of wildfires, few studies have been able to employ before-after, control-intervention experimental designs, or to evaluate fire-induced water-quality changes in the context of long-term datasets. Here, we present data from a lake draining a moorland catchment in the United Kingdom, part of a 22-site, 25 year monitoring network, which experienced a major wildfire in 2011. The main water-quality response was a large, sustained increase in nitrate concentrations, sufficient to raise acidity and aluminium concentrations, effectively reversing over a decade of recovery from the effects of acid deposition. Concurrently, we observed a clear reduction in DOC concentrations, contrasting with prescribed fire studies from similar ecosystems (none based on before-after studies) that have suggested that burning causes DOC to increase. However, data from a downstream water supply reservoir do suggest a fire-induced change in DOC quality towards more soil-derived aromatic organic compounds, and lake sediment data suggest a large increase in particulate organic carbon. We conclude that the biogeochemical responses to wildfire in our moorland catchment were broadly similar to those observed in forest ecosystems elsewhere, but that historically high nitrogen deposition has made the ecosystem particularly susceptible to nitrate leaching and (re-)acidification. The observed reduction in DOC concentrations casts some doubt on the widely held view that prescribed burning in moorland systems has contributed to long-term DOC increases.     

Dissolved organic matter quantity and quality from freshwater and saltwater lakes in east-central Alberta

Concentrations of dissolved organic matter (DOM) in surface waters of sub-humid to semi-arid lakes in east-central Alberta increase with increasing salinity and water residence time from about 20 to 330 mg L^–1 as dissolved organic carbon (DOC). This pattern is opposite to that observed among freshwater lakes spanning a gradient in water residence times, and is probably caused by evaporative concentration of refractory DOM. The proportion of total DOC, operationally defined as humic substances using XAD-8 resin, was high, though similar to surface waters typically referred to as "humic", and independent of salinity. Very long water residence times (hundreds of years) in saline lakes favors evapoconcentration of low-color, low molecular weight DOM, with N-content characteristic of allochthonous DOM.     

Chemical Characteristics and Origin of Dissolved Organic Matter in the Yukon River

Monthly (or bi-weekly) water samples were collected from the Yukon River, one of the largest rivers in North America, at a station near the US Geological Survey Stevens Village hydrological station, Alaska from May to September 2002, to examine the quantity and quality of dissolved organic matter (DOM) and its seasonal variations. DOM was further size fractionated into high molecular weight (HMW or colloidal, 1 kDa–0.45 μm) and low molecular weight (LMW, <1 kDa) fractions. Dissolved organic carbon (DOC), colored dissolved organic matter (C-DOM) and total dissolved carbohydrate (TCHO) species were measured in the size fractionated DOM samples. Concentrations of DOC were as high as 2830 μmol-C l⁻¹ during the spring breakup in May and decreased significantly to 508–558 μmol-C l⁻¹ during open-water season (June–September). Within the DOC pool, up to 85% was in the colloidal fraction (1 kDa–0.45 μm) in early May. As DOC concentration decreased, this colloidal portion remained high (70–85% of the bulk DOC) throughout the sampling season. Concentrations of TCHO, including monosaccharides (MCHO) and polysaccharides (PCHO), varied from 722 μmol-C l⁻¹ in May to 129 μmol-C l⁻¹ in September, which comprised a fairly constant portion of bulk DOC (24±2%). Within the TCHO pool, the MCHO/TCHO ratio consistently increased from May to September. The C-DOM/DOM ratio and the size fractionated DOM increased from May to September, indicating that DOM draining into the Yukon River contained increased amounts of humified materials, likely related to a greater soil leaching efficiency in summer. The average composition of DOM was 76% pedogenic humic matter and 24% aquagenic CHO. Characteristics of soil-derived humic substances and low chlorophyll-a concentrations support a dominance of terrestrial DOM in Yukon River waters.     

Three-dimensional fluorescence as a tool for investigating the dynamics of dissolved organic matter in the Lake Biwa watershed

Quantitative and qualitative characterizations of dissolved organic matter (DOM) were carried out at the watershed level in central Japan by measuring dissolved organic carbon (DOC) concentration and the three-dimensional excitation–emission matrix (3-D EEM). DOC concentration was low (mean 37 ± 19 µM C) in the upstream waters, whereas, in general, it increased toward the downstream areas (mean 92 ± 47 µM C). Significant variations in DOC concentration were detected among rivers and channels. DOC concentration in the epilimnion of Lake Biwa increased during the summer period and decreased during the winter period. The lake hypolimnion has lower DOC concentration (mean 87 ± 7 µM C) compared with the epilimnion (107 ± 15 µM C). Fulvic acid (FA)-like substances in the DOM were directly characterized by 3-D EEM. The fluorescence peak for upstream DOM was found in regions with longer wavelengths (excitation/emission 386 ± 6/476 ± 5 nm) compared with downstream and lake DOM (351 ± 12/446 ± 15 nm and 341 ± 6/434 ± 6 nm, respectively). The DOC concentration is correlated with fluorescence peak intensity of FA-like substances in DOM in river waters. Such a relationship was not found in lake DOM. A blueshift of the fluorescence peak from upstream to lake DOM was observed. A decrease in fluorescence intensities was also detected during the summer period. These results may suggest that the degradation of FA-like substances in DOM occurs from natural solar irradiation. Protein-like fluorescence was significantly detected in the lake epilimnion during the summer period. A linear relationship between DOC concentration and protein-like fluorescence indicated that an autochthonous input of DOM gave rise to the increase in DOC concentration in the lake epilimnion during the summer. These results may suggest that the 3-D EEM can be used as a tool for the investigation of DOM dynamics at the watershed level with concurrent measurement of DOC concentration and the fluorescence properties of fulvic acid-like and protein-like substances.     

华南典型树种凋落叶的野外分解和溶解性有机质溶出动态

选用华南亚热带地区常见阔叶树种木荷和针叶树种湿地松的新近凋落叶,在野外分解0、30、60、90、150、210、240、365 d,分析溶出的溶解性有机质(DOM)浓度、组成和性质的变化,以及对土壤可溶性有机碳(DOC)的影响.结果表明: 随着分解的进行,尽管木荷叶片的DOM浓度高于松针,但是2种凋落叶DOM浓度、性质和物质组成变化规律一致;2种凋落叶的DOM浓度均呈下降趋势,芳香化程度和分子量增大,富里酸、腐殖酸类物质逐渐增多,可降解的简单芳烃蛋白(如酪氨酸)逐渐减少.在分解初期,DOM主要由亲水中性和酸性部分组成,易分解、易迁移,对表层土壤DOC影响不显著;在分解后期,DOM主要为腐殖酸和富里酸类物质,吸附性强,表层土壤DOC浓度显著下降.     

Carbonate recrystallization in root-free soil and rhizosphere of Triticum aestivum and Lolium perenne estimated by 14C labeling

The photo- and bio-degradation of dissolved organic matter (DOM) in water from the Broad River were investigated in laboratory experiments using a solar simulator to control the intensity and exposure of samples to irradiation. The water samples included a natural assemblage of microorganisms, and the daily exposure of samples to irradiation was varied to distinguish the relative contributions of photochemical and biological degradation. Concentrations of dissolved organic carbon (DOC) and specific components of DOM, including chromophoric DOM (CDOM), lignin phenols and amino acids, were monitored to investigate the reactivity and predominant pathway of degradation of these DOM components. Biodegradation was primarily responsible for the overall remineralization of DOC and losses of the amino acid component of DOM, whereas photodegradation was primarily responsible for losses of the chromophoric and lignin phenol components of DOM. The rates of photodegradation of lignin phenols were strongly influenced by the presence of methoxy groups on the aryl ring. Syringyl (S) phenols have two methoxy substitutions, vanillyl (V) phenols have one methoxy substitution, and p-hydroxy (P) phenols are not substituted with methoxy groups. Photochemical decay constants were highest for S phenols, lowest for P phenols and followed a consistent pattern (S > V > P) in the experiments. The carbon-normalized yields of amino acids and lignin phenols were found to be useful molecular indicators of the highly reactive (i.e. labile) components of biodegradable and photodegradable DOM, respectively.     

Nutrient availability as major driver of phytoplankton-derived dissolved organic matter transformation in coastal environment

Incubation experiments were performed to examine the processing of fresh autochthonous dissolved organic matter (DOM) produced by coastal plankton communities in spring and autumn. The major driver of observed DOM dynamics was the seasonally variable inorganic nutrient status and characteristics of the initial bulk DOM, whereas the characteristics of the phytoplankton community seemed to have a minor role. Net accumulation of dissolved organic carbon (DOC) during the 18-days experiments was 3.4 and 9.2 µmol l^?1 d^?1 in P-limited spring and N-limited autumn, respectively. Bacterial bioassays revealed that the phytoplankton-derived DOC had surprisingly low proportions of biologically labile DOC, 12.6% (spring) and 17.5% (autumn). The optical characteristics of the DOM changed throughout the experiments, demonstrating continuous heterotrophic processing of the DOM pool. However, these temporal changes in optical characteristics of the DOM pool were not the same between seasons, indicating seasonally variable environmental drivers. Nitrogen and phosphorus availability is likely the main driver of these seasonal differences, affecting both phytoplankton extracellular release of DOM and its heterotrophic degradation by bacteria. These findings underline the complexity of the DOM production and consumption by the natural planktonic community, and show the importance of the prevailing environmental conditions regulating the DOM pathways.     

Dissolved organic matter and nutrient dynamics of a coastal freshwater forested wetland in Winyah Bay, South Carolina

Seasonally flooded, freshwater cypress-tupelo wetlands, dominated by baldcypress (Taxodium distictum), water tupelo (Nyssa aquatica), and swamp tupelo (Nyssa sylvatica var. biflora) are commonly found in coastal regions of the southeastern United States. These wetlands are threatened due to climate change, sea level rise, and coastal urban development. Understanding the natural biogeochemical cycles of nutrients in these forested wetlands as ecosystems services such as carbon sequestration and nitrogen processing can provide important benchmarks to guide conservation plans and restoration goals. In this study, surface water and soil pore water samples were collected weekly from a cypress-tupelo wetland near Winyah Bay, South Carolina and analyzed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), inorganic nitrogen, and phosphate during its flooding period between October 2010 and May 2011. DOC was further characterized by specific ultra-violet absorbance at 254 nm, spectral slope ratio (S_R) (ratio of two spectral slopes between 275–295 nm and 350–400 nm), E2/E3 ratio (ratio between A254 and A365), and fluorescence excitation-emission matrix. In addition, litterfall was collected on a monthly basis for a year while the biomass of the detritus layer (i.e., decomposed duff lying on the wetland floor) was determined before and after the flooding period. Results of the field study showed that concentrations of DOC, DON, NH₄ ⁺–N, and (NO₂ ^? + NO₃ ^?)–N in the surface water were generally higher during the fall, or peak litterfall season (October to December), than in the spring season (March to May). Highest concentrations of 54.8, 1.48, 0.270, and 0.0205 mg L^?1, for DOC, DON, NH₄ ⁺–N, and (NO₂ ^? + NO₃ ^?)–N respectively, in surface waters were recorded during October. Lower SUVA, but higher S_R and E2/E3 ratios of DOC, were observed at the end of the flooding season comparing to the initial flooding, suggesting the wetland system converts high aromatic and large DOC molecules into smaller and hydrophilic fractions possibly through photochemical oxidation. A similar trend was observed in soil pore water, but the pore water generally had greater and relatively stable concentrations of dissolved nutrients than surface water. No obvious temporal trend in phosphate concentration and total nitrogen to total phosphorus ratio (N:P) were found. Results of the laboratory extraction and mass balance calculation suggested fresh litter was a major source of DOC whereas decomposed duff was the source of dissolved nitrogen in surface water. In summary, the biogeochemistry of this isolated cypress-tupelo wetland is not only driven by the vegetation within the wetland system but also by hydrology and weather conditions such as groundwater table position, precipitation, and temperature.     

Viral lysis of Micromonas pusilla: impacts on dissolved organic matter production and composition

The viral mediated transformation of phytoplankton organic carbon to dissolved forms (“viral shunt”) has been suggested as a major source of dissolved organic carbon (DOC) in marine systems. Despite the potential implications of viral activity on the global carbon fluxes, studies investigating changes in the DOC composition from viral lysis is still lacking. Micromonas pusilla is an ecologically relevant picoeukaryotic phytoplankter, widely distributed in both coastal and oceanic marine waters. Viruses have been found to play a key role in regulating the population dynamics of this species. In this study we used axenic cultures of exponentially growing M. pusilla to determine the impact of viral lysis on the DOC concentration and composition, as estimated from lysate-derived production of transparent exopolymer particles (TEP) and two fractions of fluorescent dissolved organic matter (DOM): aromatic amino acids (excitation/emission; 280/320 nm; F(280/320)) and marine humic-like fluorescent DOM (320/410 nm; F(320/410)). DOC concentration increased 4.5 times faster and reached 2.6 times higher end concentration in the viral infected compared with the non-infected cultures. The production of F(280/320) and F(320/410) were 4.1 and 2.8 times higher in the infected cultures, and the elevated ratio between F(280/320) and F(320/410) in lysates suggested a higher contribution of labile (protein) components in viral produced DOM than in algal exudates. The TEP production was 1.8 times faster and reached a 1.5 times higher level in the viral infected M. pusilla culture compared with the non- infected cultures. The measured increase in both DOC and TEP concentrations suggests that viral lysis has multiple and opposite implications for the production and export processes in the pelagic ocean: (1) by releasing host biomass as DOC it decreases the organic matter sedimentation and promotes respiration and nutrient retention in the photic zone, whereas (2) the observed enhanced TEP production could stimulate particle aggregation and thus carbon export out of the photic zone.     

Distinct Optical Chemistry of Dissolved Organic Matter in Urban Pond Ecosystems

Urbanization has the potential to dramatically alter the biogeochemistry of receiving freshwater ecosystems. We examined the optical chemistry of dissolved organic matter (DOM) in forty-five urban ponds across southern Ontario, Canada to examine whether optical characteristics in these relatively new ecosystems are distinct from other freshwater systems. Dissolved organic carbon (DOC) concentrations ranged from 2 to 16 mg C L^-1 across the ponds with an average value of 5.3 mg C L^-1. Excitation-emission matrix (EEM) spectroscopy and parallel factor analysis (PARAFAC) modelling showed urban pond DOM to be characterized by microbial-like and, less importantly, by terrestrial derived humic-like components. The relatively transparent, non-humic DOM in urban ponds was more similar to that found in open water, lake ecosystems than to rivers or wetlands. After irradiation equivalent to 1.7 days of natural solar radiation, DOC concentrations, on average, decreased by 38% and UV absorbance decreased by 25%. Irradiation decreased the relative abundances of terrestrial humic-like components and increased protein-like aspects of the DOM pool. These findings suggest that high internal production and/or prolonged exposure to sunlight exerts a distinct and significant influence on the chemistry of urban pond DOM, which likely reduces its chemical similarity with upstream sources. These properties of urban pond DOM may alter its biogeochemical role in these relatively novel aquatic ecosystems.