No abstract

Storm events dominate riverine loads of dissolved organic carbon (DOC) and nitrate and are expected to increase in frequency and intensity in many regions due to climate change. We deployed three high‐frequency (15 min) in situ absorbance spectrophotometers to monitor DOC and nitrate concentration for 126 storms in three watersheds with agricultural, urban, and forested land use/land cover. We examined intrastorm hysteresis and the influences of seasonality, storm size, and dominant land use/land cover on storm DOC and nitrate loads. DOC hysteresis was generally anticlockwise at all sites, indicating distal and plentiful sources for all three streams despite varied DOC character and sources. Nitrate hysteresis was generally clockwise for urban and forested sites, but anticlockwise for the agricultural site, indicating an exhaustible, proximal source of nitrate in the urban and forested sites, and more distal and plentiful sources of nitrate in the agricultural site. The agricultural site had significantly higher storm nitrate yield per water yield and higher storm DOC yield per water yield than the urban or forested sites. Seasonal effects were important for storm nitrate yield in all three watersheds and farm management practices likely caused complex interactions with seasonality at the agricultural site. Hysteresis indices did not improve predictions of storm nitrate yields at any site. We discuss key lessons from using high‐frequency in situ optical sensors.

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.

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.

While recent work demonstrates that glacial meltwater provides a substantial and relatively labile flux of the micronutrient iron to oceans, the role of high-latitude estuary environments as a potential sink of glacial iron is unknown. Here we present the first quantitative description of iron removal in a meltwater-dominated estuary. We find that 85% of "dissolved" Fe is removed in the low-salinity region of the estuary along with 41% of "total dissolvable" iron associated with glacial flour. We couple these findings with hydrologic and geochemical data from Gulf of Alaska (GoA) glacierized catchments to calculate meltwater-derived fluxes of size and species partitioned Fe to the GoA. Iron flux data indicate that labile iron in the glacial flour and associated Fe minerals dominate the meltwater contribution to the Fe budget of the GoA. As such, GoA nutrient cycles and related ecosystems could be strongly influenced by continued ice loss in its watershed.

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.

Although legislation in the late 1970s significantly reduced atmospheric lead (Pb) inputs to ecosystems in North America, organic (O) horizons in forests of the northeastern USA still contain up to 30 kg of gasoline‐derived Pb ha−1 The residence time, geochemical behavior, and fate of this contaminant Pb in soils is poorly understood. Here we use forest floor time series data and synchrotron‐based X‐ray techniques to examine the mobility and speciation of Pb in O horizons collected from remote sites across the northeastern USA. At high elevation (>800 m) sites in Vermont and New York, samples collected from similar locations in 1980, 1990, and early 2000 had indistinguishable Pb contents, ranging (±1σ) from 11 to 29 kg Pb ha−1 However, at lower elevation and lower latitude sites with mixed vegetation, significant decreases in Pb amount were observed during the two‐decade study period. Lower elevation sites ranged from 10 to 20 kg Pb ha−1 in 1980, and from 2 to 10 kg Pb ha−1 20 yr later. Lead‐enriched soil grains were determined to be amorphous with microfocused X‐ray diffraction, and Pb concentrations correlated well with Fe on maps generated via microfocused X‐ray fluorescence. Bulk Pb LIII–edge X‐ray absorption spectroscopy of coniferous O horizon samples indicate that Pb is binding to iron‐rich soil particles by inner‐sphere complexes, most likely to amorphous Fe oxides. Based on our paired regional and microscopic observations, we conclude that Pb is strongly retained in well‐drained O horizons, and mobility is governed by decomposition and colloidal transport.

In the Anthropocene 1 , watershed chemical transport is increasingly dominated by novel combinations elements, which are hydrologically linked together as 'chemical cocktails.' Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water-quality problems such as toxicity to life, eutrophication, infrastructure and water treatment. A chemical cocktail approach significantly expands evaluations of water-quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water-quality violations, identify regulatory needs, and track water quality recovery following and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene.