Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

This paper is not subject to U.S. copyright. The definitive version was published in Geophysical Research Letters 38 (2011): L16605, doi:10.1029/2011GL048367.Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.We appreciate support from the USGS CMGP, NCCWSC, and the Mendenhall Postdoctoral Program

Sulfur species behavior in soil organic matter during decomposition

Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 112 (2007): G04011, doi:10.1029/2007JG000538.Soil organic matter (SOM) is a primary reservoir of terrestrial sulfur (S), but its role in the global S cycle remains poorly understood. We examine S speciation by X-ray absorption near-edge structure (XANES) spectroscopy to describe S species behavior during SOM decomposition. Sulfur species in SOM were best represented by organic sulfide, sulfoxide, sulfonate, and sulfate. The highest fraction of S in litter was organic sulfide, but as decomposition progressed, relative fractions of sulfonate and sulfate generally increased. Over 6-month laboratory incubations, organic sulfide was most reactive, suggesting that a fraction of this species was associated with a highly labile pool of SOM. During humification, relative concentrations of sulfoxide consistently decreased, demonstrating the importance of sulfoxide as a reactive S phase in soil. Sulfonate fractional abundance increased during humification irrespective of litter type, illustrating its relative stability in soils. The proportion of S species did not differ systematically by litter type, but organic sulfide became less abundant in conifer SOM during decomposition, while sulfate fractional abundance increased. Conversely, deciduous SOM exhibited lesser or nonexistent shifts in organic sulfide and sulfate fractions during decomposition, possibly suggesting that S reactivity in deciduous litter is coupled to rapid C mineralization and independent of S speciation. All trends were consistent in soils across study sites. We conclude that S reactivity is related to speciation in SOM, particularly in conifer forests, and S species fractions in SOM change during decomposition. Our data highlight the importance of intermediate valence species (sulfoxide and sulfonate) in the pedochemical cycling of organic bound S.The authors received funding for this work from the Department of Energy, National Science Foundation, and the Dartmouth College Dean of Faculty and Earth Sciences

Glacial flour dust storms in the Gulf of Alaska : hydrologic and meteorological controls and their importance as a source of bioavailable iron

Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 38 (2011): L06602, doi:10.1029/2010GL046573.Iron is an essential micronutrient that limits primary productivity in much of the ocean, including the Gulf of Alaska (GoA). However, the processes that transport iron to the ocean surface are poorly quantified. We combine satellite and meteorological data to provide the first description of widespread dust transport from coastal Alaska into the GoA. Dust is frequently transported from glacially-derived sediment at the mouths of several rivers, the most prominent of which is the Copper River. These dust events occur most frequently in autumn, when coastal river levels are low and riverbed sediments are exposed. The dust plumes are transported several hundred kilometers beyond the continental shelf into iron-limited waters. We estimate the mass of dust transported from the Copper River valley during one 2006 dust event to be between 25–80 ktons. Based on conservative estimates, this equates to a soluble iron loading of 30–200 tons. We suggest the soluble Fe flux from dust originating in glaciofluvial sediment deposits from the entire GoA coastline is two to three times larger, and is comparable to the annual Fe flux to GoA surface waters from eddies of coastal origin. Given that glaciers are retreating in the coastal GoA region and in other locations, it is important to examine whether fluxes of dust are increasing from glacierized landscapes to the ocean, and to assess the impact of associated Fe on marine ecosystems.We appreciate support from the USGS CMGP, NCCWSC, the Mendenhall postdoc program, the Woods Hole PEP intern program, and from NASA‐IDS

A New Machine-Learning Approach for Classifying Hysteresis in Suspended-Sediment Discharge Relationships Using High-Frequency Monitoring Data

Studying the hysteretic relationships embedded in high-frequency suspended-sediment concentration and river discharge data over 600+ storm events provides insight into the drivers and sources of riverine sediment during storm events. However, the literature to date remains limited to a simple visual classification system (linear, clockwise, counter-clockwise, and figure-eight patterns) or the collapse of hysteresis patterns to an index. This study leverages 3 years of suspended-sediment and discharge data to show proof-of-concept for automating the classification and assessment of event sediment dynamics using machine learning. Across all catchment sites, 600+ storm events were captured and classified into 14 hysteresis patterns. Event classification was automated using a restricted Boltzmann machine (RBM), a type of artificial neural network, trained on 2-D images of the suspended-sediment discharge (hysteresis) plots. Expansion of the hysteresis patterns to 14 classes allowed for new insight into drivers of the sediment-discharge event dynamics including spatial scale, antecedent conditions, hydrology, and rainfall. The probabilistic RBM correctly classified hysteresis patterns (to the exact class or next most similar class) 70% of the time. With increased availability of high-frequency sensor data, this approach can be used to inform watershed management efforts to identify sediment sources and reduce fine sediment export

Land Use and Season Influence Event-Scale Nitrate and Soluble Reactive Phosphorus Exports and Export Stoichiometry from Headwater Catchments

Catchment nutrient export, especially during high flow events, can influence ecological processes in receiving waters by altering nitrogen (N) and phosphorus (P) concentrations and relative amounts (stoichiometry). Event-scale N and P export dynamics may be significantly altered by land use/land cover (LULC) and season. Consequently, to manage water resources, it is important to understand how LULC and season interact to influence event N and P export. In situ, high-frequency spectrophotometers allowed us to continuously and concurrently monitor nitrate (NO3−) and soluble reactive P (SRP) concentrations and therefore examine event-scale NO3− and SRP export dynamics. Here we analyzed event NO3− and SRP concentration-discharge hysteresis patterns and yields for \u3e400 events to evaluate how LULC and seasonality influence event NO3− and SRP export dynamics in three low-order watersheds with different primary LULCs (agricultural, forested, and urban). Differences among event NO3− and SRP hysteresis patterns suggest these nutrients have different source areas and dominant transport pathways that were impacted by both LULC and seasonality. Unexpectedly, we observed similar seasonal patterns in event NO3−:SRP stoichiometry among LULCs, with the most N-enriched events occurring in spring, and event stoichiometry approaching Redfield N:P ratios in the fall. However, seasonal stoichiometry patterns were driven by unique seasonal NO3− and SRP export patterns at each site. Overall these findings suggest LULC and seasonality interact to alter the timing and magnitude of event NO3− and SRP exports, leading to seasonal patterns in event NO3− to SRP stoichiometry that may influence ecological processes, such as productivity, in receiving waters

Position of Aleutian Low Drives Dramatic Inter-Annual Variability in Atmospheric Transport of Glacial Iron to the Gulf of Alaska

Our understanding of glacial flour dust storm delivery of iron to the Gulf of Alaska (GoA) is limited. We interpret concurrent time-series satellite, meteorological, and aerosol geochemical data from the GoA to examine how inter-annual variability in regional weather patterns impacts offshore aerosol glacial iron transport. In 2011, when a northerly Aleutian Low (AL) was persistent during fall, dust emission was suppressed and highly intermittent due to prevalent wet conditions, low winds and a deep early season snowpack. Conversely, in 2012, frequent and prolonged fall dust storms and high offshore glacial iron transport were driven by dry conditions and strong offshore winds generated by persistent strong high pressure over the Alaskan interior and Bering Sea and a southerly AL. Remarkable inter-annual variability in offshore glacial aerosol iron transport indicates that the role of glacial dust in GoA nutrient cycles is likely highly dynamic and particularly sensitive to regional climate forcing

Winter weather and lake-watershed physical configuration drive phosphorus, iron, and manganese dynamics in water and sediment of ice-covered lakes

While decreasing occurrence and duration of lake ice cover is well-documented, biogeochemical dynamics in frozen lakes remain poorly understood. Here, we interpret winter physical and biogeochemical time series from eutrophic Missisquoi Bay (MB) and hyper-eutrophic Shelburne Pond (SP) to describe variable drivers of under ice biogeochemistry in systems of fundamentally different lake-watershed physical configurations (lake area, lake : watershed area). The continuous cold of the 2015 winter drove the MB sediment-water interface to the most severe and persistent suboxic state ever documented at this site, promoting the depletion of redox-sensitive phases in sediments, and an expanding zone of bottom water enriched in reactive species of Mn, Fe, and P. In this context, lake sediment and water column inventories of reactive chemical species were sensitive to the severity and persistence of subfreezing temperatures. During thaws, event provenance and severity impact lake thermal structure and mixing, water column enrichment in P and Fe, and thaw capability to suppress redox front position and internal chemical loading. Nearly identical winter weather manifest differently in nearby SP, where the small surface and watershed areas promoted a warmer, less stratified water column and active phytoplankton populations, impacting biogeochemical dynamics. In SP, Fe and P behavior under ice were decoupled due to active biological cycling, and thaw impacts were different in distribution and composition due to SP's physical structure and related antecedent conditions. We find that under ice biogeochemistry is highly dynamic in both time and space and sensitive to a variety of drivers impacted by climate change

Coupled impacts of climate and land use change across a river-lake continuum: Insights from an integrated assessment model of Lake Champlain\u27s Missisquoi Basin, 2000-2040

Global climate change (GCC) is projected to bring higher-intensity precipitation and higher-variability temperature regimes to the Northeastern United States. The interactive effects of GCC with anthropogenic land use and land cover changes (LULCCs) are unknown for watershed level hydrological dynamics and nutrient fluxes to freshwater lakes. Increased nutrient fluxes can promote harmful algal blooms, also exacerbated by warmer water temperatures due to GCC. To address the complex interactions of climate, land and humans, we developed a cascading integrated assessment model to test the impacts of GCC and LULCC on the hydrological regime, water temperature, water quality, bloom duration and severity through 2040 in transnational Lake Champlain\u27s Missisquoi Bay. Temperature and precipitation inputs were statistically downscaled from four global circulation models (GCMs) for three Representative Concentration Pathways. An agent-based model was used to generate four LULCC scenarios. Combined climate and LULCC scenarios drove a distributed hydrological model to estimate river discharge and nutrient input to the lake. Lake nutrient dynamics were simulated with a 3D hydrodynamic-biogeochemical model. We find accelerated GCC could drastically limit land management options to maintain water quality, but the nature and severity of this impact varies dramatically by GCM and GCC scenario