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At least 55 records · Page 3

Molecular Transformation of Dissolved Organic Matter during the Processes of Wildfire, Alum Coagulation, and Disinfection Using ESI(-) and ESI(+) FT-ICR MS

Forest fires alter the quality of terrestrial dissolved organic matter (DOM) flushed into source water, which could be further changed during alum coagulation and serve as potential disinfection byproduct (DBP) precursors in water facilities. To unveil this molecular transformation, we applied 12T Fourier transform ion cyclotron resonance mass spectrometry on a controlled study which used the leachates of black and white ashes (collected immediately after the 2013 Rim Fire, CA) along with unburned white fir (Abies concolor) and ponderosa pine (Pinus ponderosa). Here, results showed that the assigned features in DOM from burned ashes had a smaller molecular weight (MW), contained more unsaturated, aromatic, and oxidized and less fraction of labile compounds, and were enriched with nitrogen, relative to unburned litters. After alum coagulation, we observed the disappeared features with higher MW and S/C and N/C atom ratios than the resistant features. During the following disinfections, the disappeared features serving as the potential DBP precursors had higher MW and unsaturation degree, contained more S- and N-containing functionalities, and were more aromatic, compared to the resistant features. Our study suggested organic compounds with small MW and high aromaticity as the targets for water facilities to improve post-fire drinking water quality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupled Biotic-Abiotic Processes Control Biogeochemical Cycling of Dissolved Organic Matter in the Columbia River Hyporheic Zone

A critical component of assessing the impacts of climate change on watershed ecosystems involves understanding the role that dissolved organic matter (DOM) plays in driving whole ecosystem metabolism. The hyporheic zone—a biogeochemical control point where ground water and river water mix—is characterized by high DOM turnover and microbial activity and is responsible for a large fraction of lotic respiration. Yet, the dynamic nature of this ecotone provides a challenging but important environment to parse out different DOM influences on watershed function and net carbon and nutrient fluxes. We used high-resolution Fourier-transform ion cyclotron resonance mass spectrometry to provide a detailed molecular characterization of DOM and its transformation pathways in the Columbia river watershed. Samples were collected from ground water (adjacent unconfined aquifer underlying the Hanford 300 Area), Columbia river water, and its hyporheic zone. The hyporheic zone was sampled at five locations to capture spatial heterogeneity within the hyporheic zone. Our results revealed that abiotic transformation pathways (e.g., carboxylation), potentially driven by abiotic factors such as sunlight, in both the ground water and river water are likely influencing DOM availability to the hyporheic zone, which could then be coupled with biotic processes for enhanced microbial activity. The ground water profile revealed high rates of N and S transformations via abiotic reactions. The river profile showed enhanced abiotic photodegradation of lignin-like molecules that subsequently entered the hyporheic zone as low molecular weight, more degraded compounds. While the compounds in river water were in part bio-unavailable, some were further shown to increase rates of microbial respiration. Together, river water and ground water enhance microbial activity within the hyporheic zone, regardless of river stage, as shown by elevated putative amino-acid transformations and the abundance of amino-sugar and protein-like compounds. This enhanced microbial activity is further dependent on the composition of ground water and river water inputs. Our results further suggest that abiotic controls on DOM should be incorporated into predictive modeling for understanding watershed dynamics, especially as climate variability and land use could affect light exposure and changes to ground water essential elements, both shown to impact the Columbia river hyporheic zone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparability of Liquid Chromatography Tandem Mass Spectrometry Analysis of Dissolved Organic Matter across Laboratories

Non-targeted liquid chromatography tandem highresolution mass spectrometry (LC−MS/MS) is increasingly applied for the structure-resolved chemical analysis of dissolved organic matter (DOM). With new developments in MS instrumentation and analysis software, the approach has gained substantial momentum over the past decade. However, achieving high-quality analytical data that is reproducible and comparable across laboratories can be a bottleneck in non-targeted metabolomics and organic matter chemical analysis, especially for data reuse in repository-scale analyses. Understanding the capabilities as well as challenges of comparing LC−MS/MS data from different laboratories is necessary for inferring global trends from public data sets. To illuminate instrumentation factors that drive differences and variability, we used a standardized data analysis pipeline, including classical (CMN) and featurebased molecular networking (FBMN), to analyze data from a ring trial by 24 laboratories on identical sample sets of algal and DOM extracts that were mixed in predefined concentrations and spiked with standards. Our results showed that data sets from similar mass spectrometer types with unified instrument parameters were qualitatively comparable, resolving the same general trends and shared mass spectral features. Interlaboratory comparability was best for high-intensity features, while low-intensity features showed greater detection variability. Our analysis also highlights challenges when comparing data from instruments with different acquisition rates or operating with less standardized methods. Lastly, we provide recommendations for data integration, public data sharing, standardization, and best practices for standardized LC−MS/MS data acquisition, which will be critical for long-term time series and intercomparability of DOM chemical analyses.

DOM↗

Modeling the Dynamics and Export of Dissolved Organic Matter in the Northeastern U.S. Continental Shelf

Continental shelves are believed to play a major role in carbon cycling due to their high productivity. Particulate organic carbon (POC) burial has been included in models as a carbon sink, but we show here that seasonally produced dissolved organic carbon (DOC) on the shelf can be exported to the open ocean by horizontal transport at similar rates (1-2 mol C/sq m/yr) in the southern U.S. Mid-Atlantic Bight (MAB). The dissolved organic matter (DOM) model imbedded in a coupled circulation-biogeochemical model reveals a double dynamics: the progressive release of dissolved organic nitrogen (DON) in the upper layer during summer increases the regenerated primary production by 30 to 300%, which, in turns ; enhances the DOC production mainly from phytoplankton exudation in the upper layer and solubilization of particulate organic matter (POM) deeper in the water column. This analysis suggests that DOM is a key element for better representing the ecosystem functioning and organic fluxes in models because DOM (1) is a major organic pool directly related to primary production, (2) decouples partially the carbon and nitrogen cycles (through carbon excess uptake, POM solubilization and DOM mineralization) and (3) is intimately linked to the residence time of water masses for its distribution and export.

Druon, J.N.↗

Tidal Marsh Outwelling of Dissolved Organic Matter and Resulting Temporal Variability in Coastal Water Optical and Biogeochemical Properties

Coastal wetlands are highly dynamic environments at the land-ocean interface where human activities, short-term physical forcings and intense episodic events result in high biological and chemical variability. Long being recognized as among the most productive ecosystems in the world, tidally-influenced coastal marshes are hot spots of biogeochemical transformation and exchange. High temporal resolution observations that we performed in several marsh-estuarine systems of the Chesapeake Bay revealed significant variability in water optical and biogeochemical characteristics at hourly time scales, associated with tidally-driven hydrology. Water in the tidal creek draining each marsh was sampled every hour during several semi-diurnal tidal cycles using ISCO automated samplers. Measurements showed that water leaving the marsh during ebbing tide was consistently enriched in dissolved organic carbon (DOC), frequently by more than a factor of two, compared to water entering the marsh during flooding tide. Estimates of DOC fluxes showed a net DOC export from the marsh to the estuary during seasons of both low and high biomass of marsh vegetation. Chlorophyll amounts were typically lower in the water draining the marsh, compared to that entering the marsh during flooding tide, suggesting that marshes act as transformers of particulate to dissolved organic matter. Moreover, detailed optical and compositional analyses demonstrated that marshes are important sources of optically and chemically distinctive, relatively complex, high molecular weight, aromatic-rich and highly colored dissolved organic compounds. Compared to adjacent estuarine waters, marsh-exported colored dissolved organic matter (CDOM) was characterized by considerably stronger absorption (more than a factor of three in some cases), larger DOC-specific absorption, lower exponential spectral slope, larger fluorescence signal, lower fluorescence per unit absorbance, and higher fluorescence at visible wavelengths. Observed patterns in water optical and biogeochemical variables were very consistent among different marsh systems and throughout the year, despite continued tidal exchange, implying rapid transformation of marsh DOM in the estuary through both photochemical and microbial processes. These findings illustrate the importance of tidal marsh ecosystems as sources, sinks and/or transformers of biologically important nutrients, carbon and colored dissolved organic compounds, and their influence on short-term biological, optical and biogeochemical variability in coastal waters.

Tzortziou, Maria↗

Arctic Biogeochemical and Optical Properties of Dissolved Organic Matter Across River to Sea Gradients

Arctic landscapes are warming and becoming wetter due to changes in precipitation and the timing of snowmelt which consequently alters seasonal runoff and river discharge patterns. These changes in hydrology lead to increased mobilization and transport of terrestrial dissolved organic matter (DOM) to Arctic coastal seas where significant impacts on biogeochemical cycling can occur. Here, we present measurements of dissolved organic carbon (DOC) and chromophoric DOM (CDOM) in the Yukon River-to-Bering Sea system and two river plumes on the Alaska North Slope which flow into the Beaufort Sea. Our sampling characterized optical and biogeochemical properties of DOM during high and low river discharge periods for the Yukon River-Bering Sea system. The average DOC concentration at the multiple Yukon River mouths ranged from a high of 10.36 mg C L-1 during the ascending limb of the 2019 freshet (late May), 6.4 mg C L-1 during the descending limb of the 2019 freshet (late June), and a low of 3.86 mg C L-1 during low river discharge in August 2018. CDOM absorption coefficient at 412 nm (aCDOM(412)) averaged 8.23 m-1, 5.07 m-1, and 1.9 m-1, respectively. Several approaches to model DOC concentration based on its relationship with CDOM properties demonstrated cross-system seasonal and spatial robustness for these Arctic coastal systems despite spanning an order of magnitude decrease in DOC concentration from the lower Yukon River to the Northern Bering Sea as well as the North Slope systems. “Snapshot” fluxes of DOC and CDOM across the Yukon River Delta to Norton Sound were calculated from our measurements and modeled water fluxes forced with upstream USGS river gauge data. Our findings suggest that during high river flow, DOM reaches the delta largely unaltered by inputs or physical and biogeochemical processing and that the transformations of Yukon River DOM largely occur in the plume. However, during low summer discharge, multiple processes including local precipitation events, microbial decomposition, photochemistry, and likely others can alter the DOM properties within the lower Yukon River and Delta prior to flowing into Norton Sound.

Arctic↗

An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

Since the first detailed compositional analysis of dissolved organic matter (DOM) in 1995, high resolution mass spectrometry (HRMS) has become a vital tool for DOM characterization. While the upward trend in HRMS for molecular level analysis of DOM continues, so do the challenges of data comparison and interpretation between laboratories operating instruments of differing performance and user operating conditions. It is therefore essential that the community establishes whether data and trends can be compared robustly between research groups. To this end, 4 identically prepared DOM samples were each studied by 16 laboratories, representing 17 commercially-purchased instruments located across 8 countries, using positive- and negative-mode electrospray ionization (ESI) HRMS analysis. Despite the widely reported sensitivity of ESI experiments to sample matrix, preparation, ion source operation and instrument tuning parameters, the instruments used in this study showed relatively low variability between results for the same samples, particularly H/C and AI metrics. The variation in O/C and m/z metrics was relatively higher, although z-score graphs and %BCD demonstrated that the relative difference in general chemical composition between samples was the same for each instrument included in the study. As such, these metrics can be used for fingerprinting of DOM samples and as a benchmark for quality control in participating laboratories, with future strides in environmental science building upon these efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Chromophoric Dissolved Organic Matter on UV Inhibition of Primary Productivity in the Sea

A model was developed to assess the impact of chromophoric dissolved organic matter (CDOM) on phytoplankton production within the euphotic zone. The rate of depth-integrated daily gross primary productivity within the euphotic zone was evaluated as a function of date, latitude, CDONI absorption characteristics, chlorophyll a (chl a) concentration, vertical stratification, and phytoplankton sensitivity to UV radiation (UVR). Results demonstrated that primary production was enhanced in the upper 30 m of the water column by the presence of CDOM, where predicted increases in production due to the removal of damaging UVR more than offset its reduction resulting from the absorption of photosynthetically usable radiation. At greater depths, where little UVR remained, primary production was always reduced due to removal by CDOM of photosynthetically usable radiation. When CDOM was distributed homogeneously within the euphotic zone, the integral over z [(GPP)(sub ez)], was reduced under most bio-optical (i.e. solar zenith angle, and CDOM absorption, and ozone concentration) and photophysiological production at depth was greater than the enhancement of production at the surface.

Arrigo, Kevin R.↗

Microscale characterization of dissolved organic matter production and uptake in marine microbial mat communities

Intertidal marine microbial mats exhibited biologically mediated uptake of low molecular weight dissolved organic matter (DOM), including D-glucose, acetate, and an L-amino acid mixture at trace concentrations. Uptake of all compounds occurred in darkness, but was frequently enhanced under natural illumination. The photosystem 2 inhibitor, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea (DCMU) generally failed to inhibit light-stimulated DOM uptake. Occasionally, light plus DCMU-amended treatments led to uptake rates higher than light-incubated samples, possibly due to phototrophic bacteria present in subsurface anoxic layers. Uptake was similar with either 3H- or 14C-labeled substrates, indicating that recycling of labeled CO2 via photosynthetic fixation was not interfering with measurements of light-stimulated DOM uptake. Microautoradiographs showed a variety of pigmented and nonpigmented bacteria and, to a lesser extent, cyanobacteria and eucaryotic microalgae involved in light-mediated DOM uptake. Light-stimulated DOM uptake was often observed in bacteria associated with sheaths and mucilage surrounding filamentous cyanobacteria, revealing a close association of organisms taking up DOM with photoautotrophic members of the mat community. The capacity for dark- and light-mediated heterotrophy, coupled to efficient retention of fixed carbon in the mat community, may help optimize net production and accretion of mats, even in oligotrophic waters.

NASA Discipline Exobiology↗

Riverine dissolved organic matter transformations increase with watershed area, water residence time, and Damköhler numbers in nested watersheds

Abstract Quantifying the relative influence of factors and processes controlling riverine ecosystem function is essential to predicting future conditions under global change. Dissolved organic matter (DOM) is a fundamental component of riverine ecosystems that fuels microbial food webs, influences nutrient and light availability, and represents a significant carbon flux globally. The heterogeneous nature of DOM molecular composition and its propensity for interaction (i.e., functional diversity) can characterize riverine ecosystem function across spatiotemporal scales. To investigate fundamental drivers of DOM diversity, we collected seasonal water samples from 42 nested locations within five watersheds spanning multiple watershed sizes (~ 5 to 30,000 km 2 ) across the United States. Patterns in DOM molecular richness, aromaticity, relative abundance of N-containing formulas, and putative biochemical transformations derived from high-resolution mass spectrometry were assessed across gradients of explanatory variables associated with watershed characteristics (e.g., watershed area, water residence time, land cover). We found that putative biochemical transformations were more strongly related to explanatory variables across watersheds than common bulk DOM parameters and that watershed area, surface water residence time and derived Damköhler numbers representing DOM reactivity timescales were strong predictors of DOM diversity. The data also indicate that catchment-specific land cover factors can significantly influence DOM diversity in diverging directions. Overall, the results highlight the importance of considering water residence time and land cover when interpreting longitudinal patterns in DOM chemistry and the continued challenge of identifying generalizable drivers that are transferable across watershed and regional scales for application in Earth system models. This work also introduces a Findable Accessible Interoperable Reusable (FAIR) dataset (> 300 samples) to the community for future syntheses.

54 ENVIRONMENTAL SCIENCES↗

Molecular shifts in dissolved organic matter along a burn severity continuum for common land cover types in the Pacific Northwest, USA

Increasing wildfire severity is of growing concern in the western United States, with consequences for the production, composition, and mobilization of dissolved organic matter (DOM) from terrestrial to aquatic systems. Our current understanding of wildfire impacted DOM (often termed pyrogenic DOM) composition is largely built from temperature-based studies that can be difficult to extrapolate to field conditions, which are often defined by ‘burn severity’, or the post-wildfire impact observed at a site. Thus, burn severity can encapsulate a broader range of fire and environmental conditions not exclusive to temperature. Biogeochemical studies that describe DOM along burn severity continuums remain limited but are needed to better link DOM composition with field conditions post-fire. Here, in this study, we addressed this need with an experimental open air burn simulation that generated chars from vegetation representative of major land cover types in the western United States. The chars were leached to simulate DOM mobilization potential. The DOM composition was characterized by ultra-high resolution mass spectrometry (HR-MS) and UV/VIS absorbance and fluorescence. Our results indicated that the shifts of DOM production and composition along a burn-severity gradient depends on the land cover type that was burned, with the degree of change dependent on the composition of the starting parent vegetation material. Fluorescence signatures indicated a strong convergence across land cover types to more aromatic DOM with increasing severity, while HR-MS indicated an increase in the production of aromatic nitrogen containing DOM with increasing severity. Results from this study enhance our ability to describe DOM composition in a framework that can be more directly related with field and remote-sensing based metrics.

54 ENVIRONMENTAL SCIENCES↗

Biochemical Composition of Dissolved Organic Matter Released During Experimental Diatom Blooms

An axenic culture of Skeletonema costatum was grown to late-log phase to examine the molecular weight distribution and the biochemical composition of high molecular weight dissolved organic matter released in the absence of actively growing bacteria. A second culture was grown in a 5 m(exp 3) mesocosm and placed in darkness for a period of 51 days to examine the impact of phytoplankton bloom dynamics and microbial decomposition on dissolved (DOM) and particulate organic matter (POM) composition. DOM was separated using tangential-flow ultrafiltration into three nominal size fractions: LDOM (less than 1 kDa DOM), HDOM (1-30 kDa) and VHDOM (30 kDa-0.2 micron) and characterized. Both axenic and mesocosm diatom blooms released 28-33% of net primary production as dissolved organic carbon (DOC). In the axenic culture, HDOM and LDOM each comprised about half of the diatom-released DOC with less than l% as VHDOM. Diatoms from both experiments released carbohydrate-rich high molecular weight DOM. Much of the axenic diatom-released high molecular weight DOC could be chemically characterized (61% of HDOM and 78% of VHDOM) with carbohydrates as the primary component (45% of HDOM and 55% of VHDOM). Substantial amounts of hydrolyzable amino acids (16% of HDOM and 22% of VHDOM) and small amounts of lipids (less than 1%) were also released. Proportions of recognizable biochemical components in DOM produced in the mesocosm bloom were lower compared to the axenic culture. The presence of bacterial fatty acids and peptidoglycan-derived D-amino acids within high molecular weight fractions from the mesocosm bloom revealed that bacteria contributed a variety of macromolecules to DOM during the growth and decay of the diatom bloom. Release of significant amounts of DOC by diatoms demonstrates that DOM excretion is an important component of phytoplankton primary production. Similarities in high molecular weight DOM composition in marine waters and diatom cultures highlight the importance of phytoplankton to DOM composition in the ocean.

Mannino, Antonio↗

Drought shifts dissolved organic matter sources from above- to belowground and stress-induced processes in Amazon white-sand forests

White-sand forests contribute significantly to dissolved organic matter (DOM) production in the central Amazon, forming blackwater rivers that dominate organic matter export from the Amazon basin to the ocean. Despite their importance in controlling DOM export, white-sand forests are understudied, and it remains unclear whether systematic changes in the formation of blackwater DOM occur and how seasonal variations and extremes like El Niño-associated droughts impact them. We collected soil porewater from two central Amazon white-sand forests for two years, spanning a wet La Niña year followed by an El Niño drought year. The molecular composition of DOM was analyzed using high-resolution mass spectrometry, and correlation network analysis was employed to identify ecologically meaningful DOM subsets. Using additional chemical characterization, database annotations, correlation with 14C-age of DOM and climatic variables, and ecological null modeling, we propose five distinct DOM sources: plant litter and throughfall, soil organic matter (SOM) decomposition, root exudation, and two drought response subsets of likely microbial and plant origin. During drought conditions, aboveground plant-derived compounds decreased, while SOM products, root exudates, and drought response compounds increased. These drought responses were qualitatively similar in both years but notably amplified in the drier El Niño year. Drought amplified deterministic control over DOM composition, indicating that DOM reflected directed biological responses and that future droughts are likely to generate similar shifts. Overall, drought substantially altered belowground carbon cycling by shifting DOM sources and inducing stress responses, effects expected to recur and potentially intensify under future climate scenarios.

Lange, Dan F.↗

Competition between Dissolved Organic Matter and Freshwater Plankton Control Methylmercury Isotope Fractionation during Uptake and Photochemical Demethylation

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata. Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ199Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ~30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ 199 Hg/Δ 201 Hg ratio was uniform across experiments (~1.4), Δ 199 Hg/δ 202 Hg slopes varied dramatically (from -0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Amount and reactivity of dissolved organic matter export are affected by land cover change from old‐growth to second‐growth forests in headwater ecosystems

Abstract Headwater forest ecosystems of the western USA generate a large portion of the dissolved organic matter (DOM) transported in streams across North America. Land cover changes that alter forest structure and species composition affect the quantity and composition of DOM transferred to aquatic ecosystems. Clear‐cut harvesting affects ~1% of the forest area of North America annually, leaving most western forests in varying stages of regrowth and the total area of old‐growth forest is decreasing. The consequences of this widespread management practice on watershed carbon cycling remain unknown. We investigated the role of land cover change, because of clear‐cut harvesting, from mixed‐species old‐growth to lodgepole pine‐dominated second‐growth forest on the character and reactivity of hillslope DOM exports. We evaluated inputs of DOM from litter leachates and export of DOM collected at the base of trenched hillslopes during a 3‐year period (2016–2018) at the Fraser Experimental Forest in north‐central Colorado, USA. Dissolved organic carbon and total dissolved nitrogen were higher in lateral subsurface flow draining old‐ versus second‐growth forest. Fluorescence spectroscopy showed that the DOM exported from the old‐growth forest was more heterogeneous and aromatic and that proteinaceous, microbially processed DOM components were more prevalent in the second‐growth forest. Biological oxygen demand assays revealed much lower microbial metabolism of DOM in litter leachate and subsurface exports from the old‐growth forest relative to second growth. Old‐growth and second‐growth forests are co‐mingled in managed ecosystems, and our findings demonstrate that land cover change from a mixture of conifer species to lodgepole pine dominance influences DOM inputs that can increase the reactivity of DOM transferred from terrestrial to aquatic ecosystems.

Fegel, Timothy S.↗

Estimating the Distribution of Colored Dissolved Organic Matter During the Southern Ocean Gas Exchange Experiment Using Four-Dimensional Variational Data Assimilation

We diagnosed the effect of various physical processes on the distribution of mixed-layer colored dissolved organic matter (CDOM) and a sulfur hexauoride (SF6) tracer during the Southern Ocean Gas Exchange Experiment (SO GasEx). The biochemical upper ocean state estimate uses in situ and satellite biochemical and physical data in the study region, including CDOM (absorption coefcient and spectral slope), SF6, hydrography, and sea level anomaly. Modules for photobleaching of CDOM and surface transport of SF6 were coupled with an ocean circulation model for this purpose. The observed spatial and temporal variations in CDOM were captured by the state estimate without including any new biological source term for CDOM, assuming it to be negligible over the 26 days of the state estimate. Thermocline entrainment and photobleaching acted to diminish the mixed-layer CDOM with time scales of 18 and 16 days, respectively. Lateral advection of CDOM played a dominant role and increased the mixed-layer CDOM with a time scale of 12 days, whereas lateral diffusion of CDOM was negligible. A Lagrangian view on the CDOM variability was demonstrated by using the SF6 as a weighting function to integrate the CDOM elds. This and similar data assimilation methods can be used to provide reasonable estimates of optical properties, and other physical parameters over the short-term duration of a research cruise, and help in the tracking of tracer releases in large-scale oceanographic experiments, and in oceanographic process studies.

Del Castillo, C. E.↗

Amount and reactivity of dissolved organic matter export are affected by land cover change from old-growth to second-growth forests in headwater ecosystems

Headwater forest ecosystems of the western USA generate a large portion of the dissolved organic matter (DOM) transported in streams across North America. Land cover changes that alter forest structure and species composition affect the quantity and composition of DOM transferred to aquatic ecosystems. Clear-cut harvesting affects ~1% of the forest area of North America annually, leaving most western forests in varying stages of regrowth and the total area of old-growth forest is decreasing. The consequences of this widespread management practice on watershed carbon cycling remain unknown. We investigated the role of land cover change, because of clear-cut harvesting, from mixed-species old-growth to lodgepole pine-dominated second-growth forest on the character and reactivity of hillslope DOM exports. We evaluated inputs of DOM from litter leachates and export of DOM collected at the base of trenched hillslopes during a 3-year period (2016–2018) at the Fraser Experimental Forest in north-central Colorado, USA. Dissolved organic carbon and total dissolved nitrogen were higher in lateral subsurface flow draining old- versus second-growth forest. Fluorescence spectroscopy showed that the DOM exported from the old-growth forest was more heterogeneous and aromatic and that proteinaceous, microbially processed DOM components were more prevalent in the second-growth forest. Biological oxygen demand assays revealed much lower microbial metabolism of DOM in litter leachate and subsurface exports from the old-growth forest relative to second growth. Old-growth and second-growth forests are co-mingled in managed ecosystems, and our findings demonstrate that land cover change from a mixture of conifer species to lodgepole pine dominance influences DOM inputs that can increase the reactivity of DOM transferred from terrestrial to aquatic ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Quantification of Discharge-Specific Effects on Dissolved Organic Matter Export From Major Arctic Rivers From 1982 Through 2019

Long-term increases in Arctic river discharge have been well documented, and observations in the six largest Arctic rivers show strong positive correlations between dissolved organic carbon (DOC) concentration, river discharge, and chromophoric dissolved organic matter (CDOM) content. Here, observations of DOC and CDOM collected from 2009-2019 by the Arctic Great Rivers Observatory were used to estimate chromophoric DOC (CDOC) concentrations in the Kolyma, Lena, Mackenzie, Ob’, Yenisey, and Yukon Rivers. All rivers but the Mackenzie showed significant positive correlations between annual watershed runoff and the proportion of the DOC that is chromophoric. Historical estimates of DOC and CDOC export were calculated for 1982-2019 by extrapolating the DOC and CDOC concentration – discharge relationships from 2009-2019 as a hindcast modeled estimate. For the six rivers combined, modeled DOC and CDOC export increased, but CDOC increased faster than total DOC. The Lena and Ob’ Rivers showed significant increases in DOC export individually, with annual trends of 39.1 and 20.4 Gg C yr -1 respectively. November-April (winter) DOC and CDOC export increased in all rivers but the Yenisey, with the hindcast winter Kolyma export increasing by more than 20% per decade. There were no significant trends in discharge or associated DOC and CDOC fluxes during the observational period from 2009-2019; only when hindcasted values driven by changes in river discharge were analyzed did trends in DOC and CDOC emerge. This demonstrates how shifting seasonal distributions and increases in discharge can drive changes in DOC and CDOC concentrations and export, independent of other environmental factors.

carbon cycle↗