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At least 577 records · Page 32

Simultaneous attenuation of trace organics and change in organic matter composition in the hyporheic zone of urban streams

Trace organic compounds (TrOCs) enter rivers with discharge of treated wastewater. These effluents can contain high loads of dissolved organic matter (DOM). In a 48 h field study, we investigated changes in molecular composition of seven DOM compound classes (FTICR-MS) and attenuation of 17 polar TrOCs in a small urban stream receiving treated wastewater. Correlations between TrOCs and DOM were used to identify simultaneous changes in surface water and the hyporheic zone. Changes in TrOC concentrations in surface water ranged between a decrease of 29.2% for methylbenzotriazole and an increase of 152.2% for the transformation product gabapentin-lactam. In the hyporheic zone, only decreasing TrOC concentrations were observed, ranging from 4.9% for primidone to 93.8% for venlafaxine . TrOC attenuation coincided with a decline of molecular diversity of easily biodegradable DOM compound classes while molecular diversity of poorly biodegradable DOM compound classes increased. This concurrence indicates similar or linked attenuation pathways for biodegradable DOM and TrOCs. Strong correlations between TrOCs and DOM compound classes as well as high attenuation of TrOCs primarily occurred in the hyporheic zone. This suggests high potential for DOM turnover and TrOC mitigation in rivers if hyporheic exchange is sufficient.

54 ENVIRONMENTAL SCIENCES↗

Phosphorus availability and leaching losses in annual and perennial cropping systems in an upper US Midwest landscape

Abstract Excessive phosphorus (P) applications to croplands can contribute to eutrophication of surface waters through surface runoff and subsurface (leaching) losses. We analyzed leaching losses of total dissolved P (TDP) from no-till corn, hybrid poplar ( Populus nigra X P. maximowiczii ), switchgrass ( Panicum virgatum ), miscanthus ( Miscanthus giganteus ), native grasses, and restored prairie, all planted in 2008 on former cropland in Michigan, USA. All crops except corn (13 kg P ha −1 year −1 ) were grown without P fertilization. Biomass was harvested at the end of each growing season except for poplar. Soil water at 1.2 m depth was sampled weekly to biweekly for TDP determination during March–November 2009–2016 using tension lysimeters. Soil test P (0–25 cm depth) was measured every autumn. Soil water TDP concentrations were usually below levels where eutrophication of surface waters is frequently observed (> 0.02 mg L −1 ) but often higher than in deep groundwater or nearby streams and lakes. Rates of P leaching, estimated from measured concentrations and modeled drainage, did not differ statistically among cropping systems across years; 7-year cropping system means ranged from 0.035 to 0.072 kg P ha −1 year −1 with large interannual variation. Leached P was positively related to STP, which decreased over the 7 years in all systems. These results indicate that both P-fertilized and unfertilized cropping systems may leach legacy P from past cropland management.

54 ENVIRONMENTAL SCIENCES↗

Earlier snowmelt may lead to late season declines in plant productivity and carbon sequestration in Arctic tundra ecosystems

Arctic warming is affecting snow cover and soil hydrology, with consequences for carbon sequestration in tundra ecosystems. The scarcity of observations in the Arctic has limited our understanding of the impact of covarying environmental drivers on the carbon balance of tundra ecosystems. In this study, we address some of these uncertainties through a novel record of 119 site-years of summer data from eddy covariance towers representing dominant tundra vegetation types located on continuous permafrost in the Arctic. Here we found that earlier snowmelt was associated with more tundra net CO 2 sequestration and higher gross primary productivity (GPP) only in June and July, but with lower net carbon sequestration and lower GPP in August. Although higher evapotranspiration (ET) can result in soil drying with the progression of the summer, we did not find significantly lower soil moisture with earlier snowmelt, nor evidence that water stress affected GPP in the late growing season. Our results suggest that the expected increased CO 2 sequestration arising from Arctic warming and the associated increase in growing season length may not materialize if tundra ecosystems are not able to continue sequestering CO 2 later in the season.

54 ENVIRONMENTAL SCIENCES↗

Persistent arsenate–iron( iii ) oxyhydroxide–organic matter nanoaggregates observed in coal

Understanding how natural nanoaggregates of iron (Fe) and organic matter (OM), currently identified in organic rich soil or peat, interact with metals and metalloids is environmentally significant. Here, coal is also organic-rich and exemplifies anoxic sedimentary environments with Fe usually as pyrite and not oxides. Here, we analyze the local structure of Fe (6880–21 700 mg kg –1 ) and As (45–5680 mg kg –1 ) in representative Guizhou coal samples using X-ray absorption near-edge structure and extended X-ray absorption fine structure (XANES and EXAFS) to illustrate how Fe(III) and As(V) are preserved in coal formed from reduced, organic-rich precursors. Arsenic XANES indicates that >80% of As exists as As(V) with <14% of As associated with sulfides in 5 Guizhou coal samples, confirming published but unexplained results. An As–Fe shell at 3.25–3.29 Å in the As EXAFS suggests that this As(V) is adsorbed on Fe(III) oxyhydroxides as evidenced by Fe EXAFS in these coal samples. Significantly, lower Fe–Fe coordination numbers (CN) of 0.6–1.1 relative to those in 2-line ferrihydrite (CN = 1.6) and goethite (CN = 2.1) suggest that these Fe(III) oxyhydroxides are likely Fe–OM nanoaggregates protected by OM encapsulation and adsorption of arsenate. Such structurally stabilized composites of As(V)–Fe(III)–OM may be more widely distributed and allow oxidized As and Fe to persist in other organic-rich, reducing environments.

54 ENVIRONMENTAL SCIENCES↗

Influence of microorganisms on uranium release from mining-impacted lake sediments under various oxygenation conditions

Microbial processes can be involved in the remobilization of uranium (U) from reduced sediments under O 2 reoxidation events such as water table fluctuations. Such reactions could be typically encountered after U-bearing sediment dredging operations. Solid U(IV) species may thus reoxidize into U(VI) that can be released in pore waters in the form of aqueous complexes with organic and inorganic ligands. Non-uraninite U(IV) species may be especially sensitive to reoxidation and remobilization processes. Nevertheless, little is known regarding the effect of microbially mediated processes on the behaviour of U under these conditions.

54 ENVIRONMENTAL SCIENCES↗

A perspective on iron (Fe) in the atmosphere: air quality, climate, and the ocean

As scientists engage in research motivated by climate change and the impacts of pollution on air, water, and human health, we increasingly recognize the need for the scientific community to improve communication and knowledge exchange across disciplines to address pressing and outstanding research questions holistically. Our professional paths have crossed because our research activities focus on the chemical reactivity of Fe-containing minerals in air and water, and at the air-sea interface. (Photo)chemical reactions driven by Fe can take place at the surface of the particles/droplets or within the condensed phase. The extent and rates of these reactions are influenced by water content and biogeochemical activity ubiquitous in these systems. One of these reactions is the production of reactive oxygen species (ROS) that cause damage to respiratory organs. Another is that the reactivity of Fe and organics in aerosol particles alter surficial physicochemical properties that impact aerosol-radiation and aerosol–cloud interactions. Also, upon deposition, aerosol particles influence ocean biogeochemical processes because micronutrients such as Fe or toxic elements such as copper become bioavailable. We provide a perspective on these topics and future research directions on the reactivity of Fe in atmospheric aerosol systems, from sources to short- and long-term impacts at the sinks with emphasis on needs to enhance the predictive power of atmospheric and ocean models.

54 ENVIRONMENTAL SCIENCES↗

The diversity of aluminum-based drinking water treatment residuals for use in environmental remediation

Drinking water treatment residuals (DWTRs) are complex mixtures of organic and inorganic phases generally disposed of as waste materials. However, their strong sorptive properties could be further exploited to immobilize contaminants. To characterize these materials, we applied a range of analytical techniques to a set of aluminum-based DWTRs. Here we determined surface areas, elemental compositions using CHNS analysis and X-ray fluorescence (XRF), performed thermogravimetric analyses paired with mass spectrometry (TGA-MS), and used synchrotron-based methods: X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Elemental analyses and specific surface area measurements – that vary between 7.23 ± 0.03 and 197.6 ± 0.9 m 2 g –1 – indicate that non-coagulant additives must play an important role in controlling sorption. High resolution powder XRD reveals the presence of only a few crystalline minerals mostly derived from source waters or additives. Fe was detected by XRF in all samples, whereas Mn was present in significant levels in samples with potassium permanganate as additive. The chemical speciation of these elements was characterized by performing spectral decompositions of XAS spectra. The spectral features of Fe are consistent with iron(III) oxides/hydroxides and structural iron in clays. On the other hand, Mn is predominantly present under its reduced form, Mn(II).

54 ENVIRONMENTAL SCIENCES↗

Modulation of ENSO teleconnections over North America by the Pacific decadal oscillation

In this study, we investigate whether the Pacific decadal oscillation (PDO) can enhance or diminish El Niño Southern Oscillation (ENSO) temperature and precipitation teleconnections over North America using five single model initial-condition large ensembles (SMILEs). The use of SMILEs facilitates a statistically robust comparison of ENSO events that occur during different phases of the PDO. We find that a positive PDO enhances winter and spring El Niño temperature and precipitation teleconnections and diminishes La Niña teleconnections. A negative PDO has the opposite effect. The modulation of ENSO by the PDO is mediated by differences in the location and strength of the Aleutian Low and Pacific Jet during ENSO events under different phases of the PDO. This modulation is a simple combination of the individual effects of the PDO and ENSO over North America. Finally, we show that ENSO and the PDO can be used to evaluate the likelihood of the occurrence of temperature and precipitation anomalies in different regions, but cannot be used as a deterministic predictor of these anomalies due to the large variability between individual events.

54 ENVIRONMENTAL SCIENCES↗

Boosting Thailand’s palm oil yield with advanced seasonal predictions

Palm oil, an indispensable global commodity, plays a crucial role in Thailand's economy (Maluin et al 2020). This versatile product, found in everything from food to biodiesel and industrial applications (Kamil and Omar 2017, Chiarawipa et al 2020), cements Thailand's position as the third-largest producer in the world. The industry is particularly vital in the southern regions, where most plantations are located (Dallinger 2011), providing employment opportunities in rural areas and bolstering the nation's GDP and foreign exchange earnings through exports. However, oil palm productivity hinges on climatic conditions, with precipitation patterns being especially influential. Both local climate and remote forces like El Niño-Southern Oscillation (ENSO) significantly impact production. In neighboring Malaysia, research by Kamil and Omar (2017) has uncovered the consequential role of ENSO events on precipitation and, subsequently, palm oil productivity.

54 ENVIRONMENTAL SCIENCES↗

From pools to flow: The PROMISE framework for new insights on soil carbon cycling in a changing world

Soils represent the largest terrestrial reservoir of organic carbon, and the balance between soil organic carbon (SOC) formation and loss will drive powerful carbon-climate feedbacks over the coming century. To date, efforts to predict SOC dynamics have rested on pool-based models, which assume classes of SOC with internally homogenous physicochemical properties. However, emerging evidence suggests that soil carbon turnover is not dominantly controlled by the chemistry of carbon inputs, but rather by restrictions on microbial access to organic matter in the spatially heterogeneous soil environment. The dynamic processes that control the physicochemical protection of carbon translate poorly to pool-based SOC models; as a result, we are challenged to mechanistically predict how environmental change will impact movement of carbon between soils and the atmosphere. In this study, we propose a novel conceptual framework to explore controls on belowground carbon cycling: Probabilistic Representation of Organic Matter Interactions within the Soil Environment (PROMISE). In contrast to traditional model frameworks, PROMISE does not attempt to define carbon pools united by common thermodynamic or functional attributes. Rather, the PROMISE concept considers how SOC cycling rates are governed by the stochastic processes that influence the proximity between microbial decomposers and organic matter, with emphasis on their physical location in the soil matrix. We illustrate the applications of this framework with a new biogeochemical simulation model that traces the fate of individual carbon atoms as they interact with their environment, undergoing biochemical transformations and moving through the soil pore space. We also discuss how the PROMISE framework reshapes dialogue around issues related to SOC management in a changing world. We intend the PROMISE framework to spur the development of new hypotheses, analytical tools, and model structures across disciplines that will illuminate mechanistic controls on the flow of carbon between plant, soil, and atmospheric pools.

54 ENVIRONMENTAL SCIENCES↗

Feasibility of using distributed chemical sensing for CO2 leakage monitoring

The feasibility study focused on the development of new fiber for distributed chemical sensing (DCS) that will allow direct detection of CO 2 leakages in the environment. This is particularly important for monitoring well integrity for carbon capture and storage (CCS), to provide early warning for an incoming well failure and potential CO 2 leaking through it. We proposed using optical spectroscopy in optical fiber for direct detection of CO 2 . The main approach is based on Raman interrogation within gas-filled Holey Fibers (HoFs), so that the location and concentration of the gases would be provided simultaneously via backscattering. Additionally, Infrared (IR) Absorption Spectroscopy could also be used, and the architecture would be more discrete since interleaving with standard solid core fibers and Fiber Bragg Grating (FBG) sections is required to enable reflection to the I/O controls. The possible Raman length or the IR numbers of sections would be defined based on signal to noise ratio. The optical spectroscopy methodology would overcome current roadblocks to CCS, as fiber optics will allow for CO 2 (and other gases) detection in wells with direct in-situ measurements of concentration along with other important parameters such as temperature and pressure as the baseline of environment background.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Quantifying Variability and Controls of Riverine Dissolved Organic Carbon Exported to Arctic Coastal Margins of North America (Final Report)

This project involved implementation and application of a coupled permafrost hydrology and dissolved organic carbon process models to investigate how spatial and seasonal variations in terrestrial hydrology and soil freeze/thaw dynamics influence the mobilization, loading, and export of organic carbon to the stream network for selected arctic basins across northern Alaska and northwest Canada. The model simulations were constrained by detailed observations of in- stream chemistry, soil active layer profile moisture and temperature dynamics, streamflow, soil carbon inventories and satellite microwave remote sensing based assessments of surface soil freeze-thaw dynamics. We developed and applied the numerical modeling and data analysis, incorporating observed data for calibration and validation, in order to investigate the terrestrial hydrology, permafrost dynamics, and associated DOC production and loading to rivers across a region encompassing watersheds draining to the coast. The project produced six publications and three datasets archived in public repositories.

54 ENVIRONMENTAL SCIENCES↗

Adaptive Phenotypic Plasticity Stabilizes Evolution in Fluctuating Environments

Fluctuating environmental conditions are ubiquitous in natural systems, and populations have evolved various strategies to cope with such fluctuations. The particular mechanisms that evolve profoundly influence subsequent evolutionary dynamics. One such mechanism is phenotypic plasticity, which is the ability of a single genotype to produce alternate phenotypes in an environmentally dependent context. Here, we use digital organisms (self-replicating computer programs) to investigate how adaptive phenotypic plasticity alters evolutionary dynamics and influences evolutionary outcomes in cyclically changing environments. Specifically, we examined the evolutionary histories of both plastic populations and non-plastic populations to ask: (1) Does adaptive plasticity promote or constrain evolutionary change? (2) Are plastic populations better able to evolve and then maintain novel traits? And (3), how does adaptive plasticity affect the potential for maladaptive alleles to accumulate in evolving genomes? We find that populations with adaptive phenotypic plasticity undergo less evolutionary change than non-plastic populations, which must rely on genetic variation from de novo mutations to continuously readapt to environmental fluctuations. Indeed, the non-plastic populations undergo more frequent selective sweeps and accumulate many more genetic changes. We find that the repeated selective sweeps in non-plastic populations drive the loss of beneficial traits and accumulation of maladaptive alleles, whereas phenotypic plasticity can stabilize populations against environmental fluctuations. This stabilization allows plastic populations to more easily retain novel adaptive traits than their non-plastic counterparts. In general, the evolution of adaptive phenotypic plasticity shifted evolutionary dynamics to be more similar to that of populations evolving in a static environment than to non-plastic populations evolving in an identical fluctuating environment. All natural environments subject populations to some form of change; our findings suggest that the stabilizing effect of phenotypic plasticity plays an important role in subsequent adaptive evolution.

54 ENVIRONMENTAL SCIENCES↗

Predictability of Seawater DMS During the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES)

This work presents an overview of a unique set of surface ocean dimethylsulfide (DMS) measurements from four shipboard field campaigns conducted during the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES) project. Variations in surface seawater DMS are discussed in relation to biological and physical observations. Results are considered at a range of timescales (seasons to days) and spatial scales (regional to sub-mesoscale). Elevated DMS concentrations are generally associated with greater biological productivity, although chlorophyll a (Chl) only explains a small fraction of the DMS variability (15%). Physical factors that determine the location of oceanic temperature fronts and depth of vertical mixing have an important influence on seawater DMS concentrations during all seasons. The interplay of biomass and physics influences DMS concentrations at regional/seasonal scales and at smaller spatial and shorter temporal scales. Seawater DMS measurements are compared with the global seawater DMS climatology and predictions made using a recently published algorithm and by a neural network model. The climatology is successful at capturing the seasonal progression in average seawater DMS, but does not reproduce the shorter spatial/temporal scale variability. The input terms common to the algorithm and neural network approaches are biological (Chl) and physical (mixed layer depth, photosynthetically active radiation, seawater temperature). Both models predict the seasonal North Atlantic average seawater DMS trends better than the climatology. However, DMS concentrations tend to be under-predicted and the episodic occurrence of higher DMS concentrations is poorly predicted. The choice of climatological seawater DMS product makes a substantial impact on the estimated DMS flux into the North Atlantic atmosphere. These results suggest that additional input terms are needed to improve the predictive capability of current state-of-the-art approaches to estimating seawater DMS.

54 ENVIRONMENTAL SCIENCES↗