Modeling the sensitivity of cyanobacteria blooms to plausible changes in precipitation and air temperature variability.

Many recent studies have attributed the observed variability of cyanobacteria blooms to meteorological drivers and have projected blooms with worsening societal and ecological impacts under future climate scenarios. Nonetheless, few studies have jointly examined their sensitivity to projected changes in both precipitation and temperature variability. Using an Integrated Assessment Model (IAM) of Lake Champlain's eutrophic Missisquoi Bay, we demonstrate a factorial design approach for evaluating the sensitivity of concentrations of chlorophyll a (chl-a), a cyanobacteria surrogate, to global climate model-informed changes in the central tendency and variability of daily precipitation and air temperature. An Analysis of Variance (ANOVA) and multivariate contour plots highlight synergistic effects of these climatic changes on exceedances of the World Health Organization's moderate 50 µg/L concentration threshold for recreational contact. Although increased precipitation produces greater riverine total phosphorus loads, warmer and drier scenarios produce the most severe blooms due to the greater mobilization and cyanobacteria uptake of legacy phosphorus under these conditions. Increases in daily precipitation variability aggravate blooms most under warmer and wetter scenarios. Greater temperature variability raises exceedances under current air temperatures but reduces them under more severe warming when water temperatures exceed optimal values for cyanobacteria growth more often. Our experiments, controlled for wind-induced changes to lake water quality, signal the importance of larger summer runoff events for curtailing bloom growth through reductions of water temperature, sunlight penetration and stratification. Finally, the importance of sequences of wet and dry periods in generating cyanobacteria blooms motivates future research on bloom responses to changes in interannual climate persistence.

Watershed 'Chemical Cocktails': Forming Novel Elemental Combinations in Anthropocene Fresh Waters.

In the Anthropocene1, 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.

Atmospheric deposition of glacial iron in the Gulf of Alaska impacted by the position of the Aleutian Low.

Our understanding of glacial flour dust storm delivery of iron to the Gulf of Alaska (GoA) is limited. Here we interpret concurrent time series satellite, meteorological, and aerosol geochemical data from the GoA to examine how interannual variability in regional weather patterns impacts offshore aerosol glacial Fe deposition. 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 Fe 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. Twenty-five-fold interannual variability in regional offshore glacial aerosol Fe deposition indicates that glacial dust's impact on GoA nutrient budgets is highly dynamic and particularly sensitive to regional climate forcing.

Dynamic Coupling of Iron, Manganese, and Phosphorus Behavior in Water and Sediment of Shallow Ice-Covered Eutrophic Lakes.

Decreasing duration and occurrence of northern hemisphere ice cover due to recent climate warming is well-documented; however, biogeochemical dynamics underneath the ice are poorly understood. We couple time-series analyses of water column and sediment water interface (SWI) geochemistry with hydrodynamic data to develop a holistic model of iron (Fe), manganese (Mn), and phosphorus (P) behavior underneath the ice of a shallow eutrophic freshwater bay. During periods of persistent subfreezing temperatures, a highly reactive pool of dissolved and colloidal Fe, Mn, and P develops over time in surface sediments and bottom waters due to reductive dissolution of Fe/Mn(oxy)hydroxides below the SWI. Redox dynamics are driven by benthic O2 consumption, limited air-water exchange of oxygen due to ice cover, and minimal circulation. During thaw events, the concentration, distribution and size partitioning of all species changes, with the highest concentrations of P and "truly dissolved" Fe near the water column surface, and a relatively well-mixed "truly dissolved" Mn and "colloidal" Fe profile due to the influx of geochemically distinct river water and increased circulation. The partitioning and flux of trace metals and phosphorus beneath the ice is dynamic, and heavily influenced by climate-dependent physical processes that vary in both time and space.

Characterization of Organic Phosphorus Form and Bioavailability in Lake Sediments using P Nuclear Magnetic Resonance and Enzymatic Hydrolysis.

Lake sediments are known to be a significant source of phosphorus (P) to plankton populations under certain biogeochemical conditions; however, the contribution of sediment organic P (P) to internal P loads remains poorly understood. We investigated P speciation and bioavailability in sediments collected over multiple months from a shallow, eutrophic bay in Lake Champlain (Missisquoi Bay, VT) using solution P nuclear magnetic resonance (NMR) spectroscopy and enzymatic hydrolysis (EH) analysis of sediments collected during years with (2008) and without (2007) algal blooms. Sediments collected during bloom onset (July) and peak bloom (August) months contained the largest proportion of enzyme-labile P, whereas pre- and postbloom sediments were primarily composed of nonlabile P. Monoester P to diester P ratios changed with respect to depth, particularly during bloom periods. Monoester P and DNA accumulation, likely from settling particulate matter, began at the onset of the bloom and continued into October 2008 during the postbloom period. The disappearance of inositol hexakisphosphate stereoisomers and the generation of orthophosphate at lower sediment depths was also evident in August 2008. Principal components analysis of EH and NMR species proportions confirmed differences between sediment cores collected during bloom onset and peak bloom, compared with pre- and postbloom sediments. Large enzyme-labile and P species proportions corresponded to increased sediment P flux and reduced manganese and iron species in porewater. These findings suggest that interseasonal changes in P speciation may influence P mobility in sediments and contribute to important feedback dynamics between biological productivity and sediment water interface geochemistry.

Lead sequestration and species redistribution during soil organic matter decomposition.

The turnover of soil organic matter (SOM) maintains a dynamic chemical environment in the forest floor that can impact metal speciation on relatively short timescales. Here we measure the speciation of Pb in controlled and natural organic (O) soil horizons to quantify changes in metal partitioning during SOM decomposition in different forest litters. We provide a link between the sequestration of pollutant Pb in O-horizons, estimated by forest floor Pb inventories, and speciation using synchrotron-based X-rayfluorescence and X-ray absorption spectroscopy. When Pb was introduced to fresh forest O(i) samples, it adsorbed primarily to SOM surfaces, but as decomposition progressed over two years in controlled experiments, up to 60% of the Pb was redistributed to pedogenic birnessite and ferrihydrite surfaces. In addition, a significant fraction of pollutant Pb in natural soil profiles was associated with similar mineral phases (approximately 20-35%) and SOM (-65-80%). Conifer forests have at least 2-fold higher Pb burdens in the forest floor relative to deciduous forests due to more efficient atmospheric scavenging and slower organic matter turnover. We demonstrate that pedogenic minerals play an important role in surface soil Pb sequestration, particularly in deciduous forests, and should be considered in any assessment of pollutant Pb mobility.