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Stemflow is rainwater that runs down the trunk of trees and transport canopy derived dissolved organic matter (DOM) to the forest floor. The chemical composition of stemflow may create hot spots and hot moments of biogeochemical reactivity in the soil and water table. The amount and character of stemflow DOM throughout a 12-month period were analyzed to better understand the effect of phenophases (e.g., leafless, emergence, leafed, senescence for deciduous species and leafed-winter, emergence, leafed-spring/summer, senescence for pine) on tree-derived DOM composition. This study collected stemflow from four major species in the eastern United States, Betula lenta L. (sweet birch), Fagus grandifolia Ehrh. (American beech), Liriodendron tulipifera L. (yellow poplar), and Pinus rigida Mill. (pitch pine), on a monthly basis. A total of 157 samples were analyzed for organic carbon concentration, fluorescence, and light absorbance characteristics. Results from one of the absorbance characterizations, specific ultraviolet absorbance at 254nm, SUVA254, indicated a change in DOM composition throughout the phenophases for the four species. American beech and sweet birch increase in SUVA254 values with the lowest values occurring during emergence with progressively higher values from leafless to leafed and finally senescence phases. Pitch pine’s trend from smallest to largest values follows a different pattern beginning with leafed-winter, then leafed-spring/summer then emergence to senescence. Yellow poplar also demonstrates a different trend with no change occurring between emergence and the leafed phase with those two seasons having the smallest values, then progressively increasing in the leafless phase and then senescence. The fluorescence index (FI) values obtained demonstrate similar phenophase trends as the SUVA254 analysis except for sweet birch. The FI values for sweet birch were highest and identical in emergence and leafed, while FI successively declined between senescence and leafless phenophases. These trends indicate species and season influence sources that alter the quantity and compositional characteristics of DOM, e.g., aromatic content, which varied greatly. We are building a parallel factor analysis (PARAFAC) model based upon the total fluorescence of stemflow DOM to further investigate these changes and provide a more in-depth analysis of its chemical components throughout the different phenophases of these four trees.Funding note: This research was supported by funds from the US National Science Foundation (Award No. GCR-CMMI-1934887).

Ghost forests and abandoned farms are stark indicators of ecological change along world coastlines, caused by sea level rise (SLR). These changes adversely affect terrestrial ecosystems and economies, but expanding coastal marshes resulting from SLR also provide crucial ecosystem services such as carbon sequestration and mediate material fluxes to the ocean. We introduce a US-NSF Critical Zone Network project designed to untangle the hydrological, ecological, geomorphological, and biogeochemical processes that are altering the functioning of the marsh-upland transition in the coastal critical zone. We have instrumented six sites in the mid-Atlantic region of the US, along the coastlines of the Atlantic Ocean, Delaware Bay, and Chesapeake Bay where marshes are rapidly encroaching into forests and farmland. We have installed field sensors to observe the effects of slow hydrologic change (i.e. SLR) and fast episodic events such as high tides and storm surges on water levels, land surface elevation, salinity, redox conditions, and sap flow. We are coupling these measurements to laboratory experiments and analyses, as well as modeling to elucidate drivers and feedbacks in these complex and highly transient critical zone systems.

Many challenges remain before we can fully understand the multifaceted role that natural organic matter (NOM) plays in soil and aquatic systems. These challenges remain despite the considerable progress that has been made in understanding NOM’s properties and reactivity using the latest analytical techniques. For nearly 4 decades, the International Humic Substances Society (IHSS, which is a non-profit scientific society) has distributed standard substances that adhere to strict isolation protocols and reference materials that are collected in bulk and originate from clearly defined sites. These NOM standard and reference samples offer relatively uniform materials for designing experiments and developing new analytical methods. The protocols for isolating NOM, and humic and fulvic acid fractions of NOM utilize well-established preparative scale column chromatography and reverse osmosis methods. These standard and reference NOM samples are used by the international scientific community to study NOM across a range of disciplines from engineered to natural systems, thereby seeding the transfer of knowledge across research fields. Recently, powerful new analytical techniques used to characterize NOM have revealed complexities in its composition that transcend the “microbial” vs. “terrestrial” precursor paradigm. To continue to advance NOM research in the Anthropocene epoch, a workshop was convened to identify potential new sites for NOM samples that would encompass a range of sources and precursor materials and would be relevant for studying NOM’s role in mediating environmental and biogeochemical processes. We anticipate that expanding the portfolio of IHSS reference and standard NOM samples available to the research community will enable this diverse group of scientists and engineers to better understand the role that NOM plays globally under the influence of anthropogenic mediated changes.

Triclosan (TCS) is an antimicrobial compound found in many household products used across the world. TCS is not completely removed in wastewater systems, resulting in trace-level concentrations present ubiquitously in surface waters. The direct photodegradation of TCS has been widely studied, with results indicating that TCS breaks down to chlorophenols and dioxins. To date, no studies have specifically investigated the effects of alkalinity on the photolysis of the acidic form of TCS. This study assessed the effect of carbonate/bicarbonate alkalinity, which is ubiquitous in natural waters, on the photolysis rate of TCS. Results indicate that bicarbonate enhances the photodegradation of TCS at pH values well below the pKa of TCS (7.9), with direct photolysis reaction kinetics that are very slow in the absence of buffers, but significant in the presence of bicarbonate (0.711 h−1 at pH 6.55). At pH values well above its pKa, both unbuffered- and buffered-mediated photolysis increased dramatically (1.92 h−1 for direct photolysis and 2.86 h−1 in buffered water) and is attributable to the increased photoreactivity of TCS by its conjugate base. Photolysis of methyl triclosan (MeTCS), a non-acidic analog of TCS, demonstrated the importance of TCS’s acidic functionality as MeTCS did not degrade at any pH. The observed influence of alkalinity on the acidic form of TCS photolysis was attributed to both a decrease in its excited state pKa, coupled with TCS deprotonation through an excited state proton transfer to a base (bicarbonate and to a lesser degree hydrogen phosphate) resulting in the more photo-labile conjugate base form of TCS.

Fe(II) has been extensively studied due to its importance as a reductant in biogeochemical processes and contaminant attenuation. Previous studies have shown that ligands can alter aqueous Fe(II) redox reactivity but their data interpretation is constrained by the use of probe compounds. Here, we employed mediated electrochemical oxidation (MEO) as an approach to directly quantify the extent of Fe(II) oxidation in the absence and presence of three model organic ligands (citrate, nitrilotriacetic acid, and ferrozine) across a range of potentials (

Redox active species in Arctic lacustrine sediments play an important, regulatory role in the carbon cycle, yet there is little information on their spatial distribution, abundance, and oxidation states. Here, we use voltammetric microelectrodes to quantify the

Acid mine drainage (AMD) formed from pyrite (iron disulfide) weathering contributes to ecosystem degradation in impacted waters. Solar irradiation has been shown to be an important factor in the biogeochemical cycling of iron in AMD-impacted waters, but its impact on dissolved organic matter (DOM) is unknown. With a typical AMD-impacted water (pH 2.7-3) collected from the Perry State Forest watershed in Ohio, we observed highly efficient (>80%) photochemical mineralization of DOM within hours in a solar simulator resembling twice summer sunlight at 40°N. We confirmed that the mineralization was initially induced by •OH formed from FeOH2+ photodissociation and was inhibited 2-fold by dissolved oxygen removal, suggesting the importance of both the photochemical reaction and oxygen involvement. Size exclusion chromatography and Fourier transform ion cyclotron resonance mass spectrometry elucidated that any remaining organic matter was comprised of smaller and highly aliphatic compounds. The quantitative and qualitative changes in DOM are likely to constitute an important component in regional carbon cycling and nutrient release and to influence downstream aquatic ecosystems in AMD-affected watersheds.

The ice-covered period in lakes is increasingly recognized for its unique hydrodynamic and biogeochemical phenomena and ecological relevance yet it remains poorly studied compared to the ice-free season. Knowledge gaps exist where research areas – hydrodynamics, biogeochemistry and biology – intersect. For example, density-driven circulation under ice coincides with an expansion of the anoxic zone, but abiotic and biotic controls on oxygen depletion have not been disentangled. While heterotrophic microorganisms and migrating phytoplankton often thrive at the oxycline, the extent to which physical processes induce fluxes of heat and substrates that further support under-ice food webs is uncertain. Similarly, radiatively-driven convection under ice in spring can promote growth of motile phytoplankton or diatoms depending on flow velocity, water clarity and mixing depth, but links between functional trait selection, trophic transfer to zooplankton and fish and the prevalence of microbial versus classical food webs in seasonally ice-covered lakes remain unclear. Under-ice processes cascade into and from the ice-free season, and are relevant to annual cycling of energy and carbon through aquatic food webs. Understanding the coupling between state transitions and the reorganization of trophic hierarchies is essential for predicting complex ecosystem responses to climate change. In this presentation, we briefly review existing knowledge regarding physical processes in lakes in winter and the parallel developments in under-ice biogeochemistry and ecology. We then illustrate interactions between these processes, identify extant knowledge gaps whose solution requires interdisciplinary approaches, and present (novel) methods to address outstanding questions.

Iron (Fe) plays a critical role in the formation of hydroxyl radical ( OH) which may participate in the indirect photodegradation of aquatic contaminants. While Fe photochemistry has been extensively studied, the efficacy of iron amendments for contaminant attenuation in sunlit natural waters has not been well researched. We studied the efficacy of this approach by monitoring OH induced acetochlor (AC) degradation and determining OH production rates with terephthalate (TPA) as a probe. Surface wetland waters as well as model fulvic acid (FA) solutions were amended with Fe(III) salt at different concentrations at pH values of 2.7, 5, and 7.6. We observed no significant enhancement in the AC degradation rate at circumneutral pH. At pH 5, AC degradation increased by more than 50% with an Fe addition up to an [Fe]T ≈ 6 μM and plateaued at high [Fe]T. At the highly acidic pH of acid mine drainage (AMD) waters, AC degradation was enhanced by two-orders-of magnitude with increasing [Fe]T and no plateau was observed under the conditions tested ([Fe]T ≤ 500 μM). While the Fe induced relative difference in OH production rates determined using TPA was useful in elucidating the reaction mechanism for different dissolved organic matter types at different pH values, the absolute value of OH production rates over-predicted the transformation of AC suggesting the existence of unknown side reactions and/or alternative reactive intermediates.

We investigated concurrent effects between nano-sized zero-valent iron (NZVI) and dissolved organic matter (DOM). Specific UV absorbance of DOM revealed that aromatic/hydrophobic moieties of DOM were bounded to NZVI surfaces. The DOM fluorescence emission peak shifted toward lower wavelength after NZVI exposure, which indicated removal of aromatic DOM fractions. This blue shift of the emission peak also attributes to the reduction of electron acceptors through NZVI-DOM charge transfer complexes. High molecular weight (103-104 Da) DOM fractions, which are suspected to be both aromatic and hydrophobic, were removed. X-ray absorption spectroscopy (XAS) elucidated that Fe(0) content in the 30-d aged NZVI in the presence of DOM (61.6%) was substantially higher than that in the absence of DOM (25.0%). Corrosion and oxidation of NZVI were mitigated due to interruption of electron transfer by surface bounded DOM and stabilization of Fe(II) by Fe-DOM complexes. The XAS also revealed that the evolution of the iron (oxyhydr)oxide shell of NZVI was significantly altered by complexed aromatic DOM.

Triclocarban (TCC) is a common antimicrobial compound used in soaps and other household products and is found globally in many surface waters. This study investigated the acute toxicity of TCC and its photolyzed products to Daphnia magna using 50% 96-h lethal concentration (LC50) tests. The effects of dissolved organic matter (DOM) on the toxicity of TCC photoproducts to D. magna were also studied. Direct photolysis of TCC formed photoproducts that were significantly less toxic (LC50 value of 2.67 ± 0.6 μM) than the parent TCC compound (LC50 value of 0.087 ± 0.3 μM). In contrast, the indirect photolysis of TCC in the presence of DOM produced photoproducts that were significantly more toxic (LC50 value of 0.032 ± 0.015 μM). Chlorinated anilines and isocyanates, identified by mass spectrometry, were formed in the presence of DOM as indirect photolysis products of TCC and were shown to be partially responsible for the observed toxicity.

Organic UV-filters are key ingredients found in sunscreens, cosmetics and plastic goods. Concerns have been raised about potential ecological and human health effects of certain organic UV filters that are currently FDA approved for use in the United States. Here, we investigate the photochemical fate of two of these compounds, oxybenzone and sulisobenzone. Both oxybenzone and sulisobenzone have previously been detected in surface waters, seawater, and treated wastewater effluent. Direct photolysis is found to be unimportant for these compounds, however, enhanced photodegradation of oxybenzone and sulisobenzone was observed under simulated solar irradiation in solutions of International Humic Substance Society standards (Pony Lake fulvic acid and Suwannee River natural organic matter), filtered wastewater effluent (Southerly Wastewater Treatment Plant in Lockbourne, OH), and Scioto River water (Columbus, OH) at pH 7. Quenching experiments with isopropanol revealed that the main pathway for degradation appears to be reaction with the hydroxyl radical (OH). Observed degradation rates were 2–3 times slower than estimates calculated using literature reported second-order rate constants and measured hydroxyl radical steady-state concentrations for Suwannee River natural organic matter, Pony Lake fulvic acid and Scioto waters. The Southerly sample, however, exhibited nearly identical expected and observed rate constants, which we take to indicate the presence of unidentified reactive species that can react with oxybenzone and sulisobenzone. Values obtained in this work were used to calculate second-order rate constants for oxybenzone and sulisobenzone with the hydroxyl radical, as well as to estimate environmental half-lives for these compounds. Near surface 24-h averaged half-lives of 3.0 and 4.0 days were calculated for oxybenzone and sulisobenzone, respectively. When extrapolated to an environmentally representative water column, these same 24-h averaged half-lives increased to 2.4 and 3.5 years, respectively.

The photoreactivity of treated wastewater effluent organic matter differs from that of natural organic matter, and the indirect phototransformation rates of micropollutants originating in wastewater are expected to depend on the fractional contribution of wastewater to total stream flow. Photodegradation rates of four common compounds of wastewater origin (sulfamethoxazole, sulfadimethoxine, cimetidine and caffeine) were measured in river water, treated municipal wastewater effluent and mixtures of both to simulate various effluent-stream water mixing conditions that could occur in environmental systems. Compounds were chosen for their unique photodegradation pathways with the photochemically produced reactive intermediates, triplet-state excited organic matter (3OM*), singlet oxygen (1O2), and hydroxyl radicals (OH). For all compounds, higher rates of photodegradation were observed in effluent relative to upstream river water. Sulfamethoxazole degraded primarily via direct photolysis, with some contribution from OH and possibly from carbonate radicals and other unidentified reactive intermediates in effluent-containing samples. Sulfadimethoxine also degraded mainly by direct photolysis, and natural organic matter appeared to inhibit this process to a greater extent than predicted by light screening. In the presence of effluent organic matter, sulfadimethoxine showed additional reactions with OH and 1O2. In all water samples, cimetidine degraded by reaction with 1O2 (>95%) and caffeine by reaction with OH (>95%). In river water mixtures, photodegradation rate constants for all compounds increased with increasing fractions of effluent. A conservative mixing model was able to predict reaction rate constants in the case of hydroxyl radical reactions, but it overestimated rate constants in the case of 3OM* and 1O2 pathways. Finally, compound degradation rate constants normalized to the rate of light absorption by water correlated with E2/E3 ratios (sample absorbance at 254 nm divided by sample absorbance at 365 nm), suggesting that organic matter optical properties may hold promise to predict indirect compound photodegradation rates for various effluent mixing ratios.

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

To study the structure and function of soil organic matter, soil scientists have performed alkali extractions for soil humic acid (HA) and fulvic acid (FA) fractions for more than 200 years. Over the last few decades aquatic scientists have used similar fractions of dissolved organic matter, extracted by resin adsorption followed by alkali desorption. Critics have claimed that alkali-extractable fractions are laboratory artifacts, hence unsuitable for studying natural organic matter structure and function in field conditions. In response, this review first addresses specific conceptual concerns about humic fractions. Then we discuss several case studies in which HA and FA were extracted from soils, waters, and organic materials to address meaningful problems across diverse research settings. Specifically, one case study demonstrated the importance of humic substances for understanding transport and bioavailability of persistent organic pollutants. An understanding of metal binding sites in FA and HA proved essential to accurately model metal ion behavior in soil and water. In landscape-based studies, pesticides were preferentially bound to HA, reducing their mobility. Compost maturity and acceptability of other organic waste for land application were well evaluated by properties of HA extracted from these materials. A young humic fraction helped understand N cycling in paddy rice (Oryza sativa L.) soils, leading to improved rice management. The HA and FA fractions accurately represent natural organic matter across multiple environments, source materials, and research objectives. Studying them can help resolve important scientific and practical issues.

Isoproturon (IPU) is a phenylurea herbicide used to control broad-leaf grasses on grain fields. Photosensitized transformation induced by excited triplet states of dissolved organic matter (3DOM*) has been identified as an important degradation pathway for IPU in sunlit waters, but the reappearance of IPU in the absence of light is observed after the initial photolysis. In this study, we elucidate the kinetics of this photodegradation and dark-reappearance cycling of IPU in the presence of DOM proxies (aromatic ketones and reference fulvic acids). Using mass spectrometry and nuclear magnetic resonance spectroscopic techniques, a semi-stable intermediate (IPUint) was found to be responsible for IPU reversion and was identified as a hydroperoxyl derivative of IPU. IPUint is photogenerated from incorporation of diatomic oxygen to IPU and is subjected to thermolysis whose rate depends on temperature, pH, the presence of DOM, and inorganic ions. These results are important to understand the overall aquatic fat...

Supraglacial streams are important hydrologic features in glaciated environments as they are conduits for the transport of aeolian debris, meltwater, solutes and microbial communities. We characterized the basic geomorphology, hydrology and biogeochemistry of the Cotton Glacier supraglacial stream located in the McMurdo Dry Valleys of Antarctica. The distinctive geomorphology of the stream is driven by accumulated aeolian sediment from the Transantarctic Mountains, while solar radiation and summer temperatures govern melt in the system. The hydrologic functioning of the Cotton Glacier stream is largely controlled by the formation of ice dams that lead to vastly different annual flow regimes and extreme flushing events. Stream water is chemically dilute and lacks a detectable humic signature. However, the fluorescent signature of dissolved organic matter (DOM) in the stream does demonstrate an extremely transitory red-shifted signal found only in near-stream sediment leachates and during the initial flushing of the system at the onset of flow. This suggests that episodic physical flushing drives pulses of DOM with variable quality in this stream. This is the first description of a large Antarctic supraglacial stream and our results provide evidence that the hydrology and geomorphology of supraglacial streams drive resident microbial community composition and biogeochemical cycling.

Isolation of organic molecules directly from Paleozoic to Cenozoic fossils has been documented, which raises important, new questions about the conditions of preservation and the range of paleobiological issues that can be addressed with these new data. Herein, molecules are isolated from fossil echinoderms exceeding 445 Ma in age. Previously, morphological data have been insufficient to establish a consensus regarding early echinoderm evolution. Thus, organic molecules extracted from fossil echinoderm specimens (mostly Paleozoic) belonging to the classes Asteroidea, Blastoidea, Crinoidea, Diploporita, Echinoidea, and Edrioasteroidea are used to assess the position of crinoids and blastozoans within competing echinoderm phylogenetic hypotheses. Fluorescence excitation-emission spectroscopy of organic molecules in fossil extracts are used to compare relationships among hypotheses. These new data support the hypothesis that living eleutherozoans diverged early from stemmed echinoderms, crinoids are nested within the clade that includes other blastozoans, and edrioasteroids are a distinct clade.

Urban geochemistry is a unique discipline that is distinguished from general geochemistry by the complex infrastructure and intense human activities associated with concentrated population centers. As stated by Thornton (1991) “This subject is concerned with the complex interactions and relationships between chemical elements and their compounds in the urban environment, the influence of past and present human and industrial activities on these, and the impacts or effects of geochemical parameters in urban areas on plant, animal and human health.” Urban areas present special challenges to geochemists attempting to understand geochemical states and fluxes. On the 5–6 of August, 2014, the first meeting of the reorganized Urban Geochemistry Working Group of the International Association of GeoChemistry (IAGC) was held in Columbus, Ohio, United States. Two goals of the meeting were to develop the overall scope, and a general definition of urban geochemistry. Five grand themes were developed: 1) recognizing the urban geochemical signature; 2) recognizing the legacy of altered hydrologic and geochemical cycles in urban environments; 3) measuring the urban geochemical signature; 4) understanding the urban influence on geochemical cycles from the continuous development and erosion of physical infrastructure and episodic perturbations; and 5) relating urban geochemistry to human and environmental health and policy. After synthesizing the discussion of these themes we offer the following perspective on the science of urban geochemistry building on the work of Thornton (1991): Urban geochemistry as a scientific discipline provides valuable information on the chemical composition of environments that support large populations and are critical to human health and well-being. Research into urban geochemistry seeks to 1) elucidate and quantify the sources, transport, transformations, and fate of chemicals in the urban environment, 2) recognize the spatial and temporal (including legacies) variability in these processes, and 3) integrate urban studies into global perspectives on climate change, biogeochemical cycles, and human and ecosystem health. We hope that this discussion will encourage other geochemists to engage in challenges unique to urban systems, as well as provide a framework for the future of urban geochemistry research.

Mercury/gold amalgam and bismuth film electrodes (BiFEs) were used to make the first centimeter-scale measurements of redox species in benthic pore waters of prairie pothole wetlands across a hydrologic gradient. Sulfide in pore waters increased across this system from negligible sulfide in hydrologically up-gradient recharge wetlands to thousands of micromolar in down-gradient discharge wetlands. Field measurements of sulfides using the BiFE were tested against an established colorimetric assay. Sulfide measured with the BiFE agreed well with colorimetric measurements but is not subject to analytical artifacts associated with methods needed to extract the pore waters. Use of Hg/Au and BiFE electrodes should allow for rapid in situ detection of redox active species, especially sulfide concentrations of >500 μM, in pore waters over seasonal to decadal time scales. Such measurements are needed to understand important biogeochemical and environmental processes such as carbon cycling and contaminant attenuati...

We reassessed the molecular weight of dissolved organic matter (DOM) determined by high pressure size exclusion chromatography (HPSEC) using measurements made with different columns and various generations of polystyrenesulfonate (PSS) molecular weight standards. Molecular weight measurements made with a newer generation HPSEC column and PSS standards from more recent lots are roughly 200 to 400 Da lower than initial measurements made in the early 1990s. These updated numbers match DOM molecular weights measured by colligative methods and fall within a range of values calculated from hydroxyl radical kinetics. These changes suggest improved accuracy of HPSEC molecular weight measurements that we attribute to improved accuracy of PSS standards and changes in the column packing. We also isolated DOM from wetlands in the Prairie Pothole Region (PPR) using XAD-8, a cation exchange resin, and PPL, a styrene-divinylbenzene media, and observed little difference in molecular weight and specific UV absorbance at 280 nm (SUVA

Soil-air partition coefficient (Ksoil-air) values are often employed to investigate the fate of organic contaminants in soils; however, these values have not been measured for many compounds of interest, including semivolatile current-use pesticides. Moreover, predictive equations for estimating Ksoil-air values for pesticides (other than the organochlorine pesticides) have not been robustly developed, due to a lack of measured data. In this work, a solid-phase fugacity meter was used to measure the Ksoil-air values of 22 semivolatile current- and historic-use pesticides and their degradation products. Ksoil-air values were determined for two soils (semiarid and volcanic) under a range of environmentally relevant temperature (10-30 °C) and relative humidity (30-100%) conditions, such that 943 Ksoil-air measurements were made. Measured values were used to derive a predictive equation for pesticide Ksoil-air values based on temperature, relative humidity, soil organic carbon content, and pesticide-specific octanol-air partition coefficients. Pesticide volatilization losses from soil, calculated with the newly derived Ksoil-air predictive equation and a previously described pesticide volatilization model, were compared to previous results and showed that the choice of Ksoil-air predictive equation mainly affected the more-volatile pesticides and that the way in which relative humidity was accounted for was the most critical difference.

Electron donating capacity (EDC) values were determined for a set of pore water samples collected from the sediments of four separate wetlands in the Cottonwood Lakes Study Area in Jamestown, ND by mediated electrochemical analysis, reaction with substituted nitro(so)benzenes, and calculation based on measured organic carbon and sulfide concentrations. The samples were taken from four hydrologically connected and increasingly sulfidic wetlands within the study site. Parallel trends in EDC values related to hydrologic conditions and to in situ reduced sulfur content were observed by all three methodologies. In particular, it was found that sulfide and dissolved organic matter (DOM) are the primary and secondary reductants, respectively, in these systems. The efficacy of these reductants in transforming organic contaminants, however, is largely driven by native pore water reduced sulfur content. Manipulation of the systems demonstrate that while DOM is capable of reducing highly oxidized contaminants or reactive intermediates, this likely only occurs once the reducing capacity of the sulfide is exhausted. Sulfide therefore was the dominant electron donor in the pore water samples.

Wetlands in the prairie pothole region of North America, which are among the most threatened ecosystems in the world, provide many services, ranging from waterfowl habitats to pesticide attenuation to carbon sequestration. The dissolved organic matter (DOM) that occurs within these wetlands, in surface waters and sediment porewaters, was examined by molecular-level techniques. While it contains components typical of DOM from surface and subsurface waters, both sulfidic and nitrogenous organic molecules are significantly more abundant in this DOM pool than in other natural waters and show distribution patterns that exactly mimic the pattern observed for DOM that is comprised of only carbon, hydrogen, and oxygen. This indicates that incorporation of N and S within DOM is abiotic and nonspecific, likely involving hydrogen sulfide, polysulfides, and N-containing nucleophiles.

Photolytic transformation of organic contaminants in wetlands can be mediated by chromophoric dissolved organic matter (CDOM), which in turn can lose its reactivity from photobleaching. We collected water from a small agricultural wetland (Ohio), Kawai Nui Marsh (Hawaii), the Everglades (Florida), and Okefenokee Swamp (Georgia) to assess the effect of photobleaching on the photofate of two herbicides, acetochlor and isoproturon. Analyte-spiked water samples were irradiated using a solar simulator and monitored for changes in CDOM light absorbance and dissolved oxygen. Photobleaching did not significantly impact the indirect photolysis rates of either herbicide over 24 hours of irradiation. Surprisingly, the opposite effect was observed with isoproturon, which accelerated DOM photobleaching. This phenomenon was more pronounced in higher-CDOM waters, and we believe that the redox pathway between triplet-state CDOM and isoproturon may be responsible for our observations. By contrast, acetochlor indirect photolysis was dependent on reaction with the hydroxyl radical and did not accelerate photobleaching of wetland water as much as isoproturon. Finally, herbicide indirect photolysis rate constants did not correlate strongly to any one chemical or optical property of the sampled waters.

In agricultural fields, crop plants may transform or degrade hormonally active compounds in manure used as fertilizer and thereby affect the overall endocrine-disrupting activity of agricultural runoff. This study examined the transformation of two natural steroid estrogens [17β-estradiol (17β-E2) and estrone (E1)] and two synthetic estrogen mimics [zeranol (α-ZAL) and zearalanone (ZAN)] by maize seedlings. Growing whole maize seedlings in hydroponic solutions of target estrogens resulted in both oxidative (i.e., 17β-E2 to E1 and α-ZAL to ZAN) and reductive (i.e., E1 to 17β-E2 and ZAN to α-ZAL) transformations. Although all four estrogens accumulated in maize roots as both parents and products, the shoots contained only 17β-E2 and α-ZAL, regardless of whether they were the parent or the product. Crude plant enzyme extracts led to substantial reductive transformations but created only trace amounts of oxidation products. In contrast, only oxidative transformations occurred in solutions exposed to plant-associated microbes. Thus, the combined effects of plant enzymes and plant-associated microbes account for the reversible transformations observed with whole plants. These effects are expected to generally decrease the overall estrogenicity of runoff from manure-fertilized fields.

Sediment pore-water dissolved organic matter (DOM) in two North Dakota prairie pothole lakes was quantified by dissolved organic carbon analysis (DOC) and its composition was characterized as a function of sediment depth for molecular weight distribution (MWD), molar absorptivity at 280 nm (ɛ280), and fluorescence properties. Fluorescence excitation emission matrices were further analyzed by creating a Parallel Factor Analysis (PARAFAC) model specific to sedimentary pore-water DOM. The range of absolute pore-water DOC concentrations (∼ 26–183 mg C L−1) greatly exceeded abundances reported for other wetlands and generally increased with depth. Significant changes occurred in ɛ280 and fluorescence seasonally. Prairie pothole pore-water DOM is primarily allochthonous in nature and three ‘humic-like’ components explained ∼ 90% of total sample fluorescence, while a single ‘non-humic’ component was responsible for the remaining 10%. The contribution of the non-humic component, however, was more significant in the top 7 cm of sediment in samples collected in early autumn and is presumably derived from algal precursor material produced by primary production in the water column over the summer. The PARAFAC results corroborate ɛ280 and MWD changes in pore-water DOM composition over the growing season. This dynamic process could affect the type of DOM available for biogeochemical processes seasonally.

Pony Lake, at Cape Royds, Antarctica, is a shallow, eutrophic, coastal lake that freezes solid in the winter. Changes in Pony Lake's physicochemical parameters and microbial community were studied during the transition from ice to open water. Due to rising water temperatures, the progressive melt of the ice column and the gradual mixing of basal brines into the remaining water column, Pony Lake evolved physically and chemically over the course of the summer, thereby affecting the microbial community composition. Temperature, pH, conductivity, nutrients and major ion concentrations reached their maximum in January. Pony Lake was colonized by bacteria, viruses, phytoflagellates, ciliates, and a small number of rotifers. Primary and bacterial production were highest in mid-December (2.66 mg C l-1d-1and 30.5 μg C l-1d-1, respectively). A 16S rRNA gene analysis of the bacterioplankton revealed 34 unique sequences dominated by members of theβ- andγ-proteobacterialineages. Cluster analyses on denaturing gradient gel electrophoresis (DGGE) banding patterns and community structure indicated a shift in the dominant members of the microbial community during the transition from winter ice, to early, and late summer lakewater. Our data demonstrate that temporal changes in physicochemical parameters during the summer months determine community dynamics and mediate changes in microbial species composition.

Biomarkers and other ancient preserved molecules are rapidly being discovered and used to study the evolution of life on Earth. We report the existence of echinoderm-specific organic molecules from different lower Mississippian (340 Ma) crinoid species that occur in the same sedimentary bed. These are the oldest examples of biomarker molecules extracted directly from fossilized remains. These biomarker molecules appear to resemble aromatic or polyaromatic quinones, based upon ultraviolet and visible light spectroscopy, fluorescence excitation-emission matrix spectroscopy, and electrospray ionization time-of-flight mass spectrometry. Results suggest that the preservation of diagnostic organic molecules is much more common that previously realized, and that preserved organic molecules may provide an independent method to unravel phylogenetic relationships among echinoderms and, perhaps, other fossilized organisms.

Non-point source pesticide pollution is a concern for wetlands in the prairie pothole region (PPR). Recent studies have demonstrated that reduced sulfur species (e.g., bisulfide and polysulfides) in PPR wetland pore waters directly undergo reactions with chloroacetanilide and dinitroaniline compounds. In this paper, the abiotic transformation of two organophosphate compounds, chlorpyrifos and chlorpyrifos-methyl, was studied in PPR wetland pore waters. Chlorpyrifos-methyl reacted significantly faster (up to 4 times) in pore water with reduced sulfur species relative to hydrolysis. No rate enhancement was observed in the transformation of chlorpyrifos in pore water with reduced sulfur species. The lack of reactivity was most likely caused by steric hindrance from the ethyl groups and partitioning to dissolved organic matter (DOM), thereby shielding chlorpyrifos from nucleophilic attack. Significant decreases in reaction rates were observed for chlorpyrifos in pore water with high concentrations of DOM. Rate enhancement due to other reactive species (e.g., organo-sulfur compounds) in pore water was minor for both compounds relative to the influence of bisulfide and DOM.

Brominated flame-retardants (BFRs) can be released from consumer products, resulting in accumulation in the surrounding environment and/or long-range transport to remote environments. We evaluated concentration changes in a suite of BFRs, including 13 polybrominated diphenyl ethers (PBDEs) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in air at Toolik Lake, Arctic Alaska during the Northern Hemisphere summer of 2013. A high-volume active air sampler was used to collect 2 day integrated samples at the field station and three flow-through air samplers were used to collect 18 day integrated samples along a transect extending away from the field station. The BDE congeners associated with the penta-BDE commercial mixture (BDE-47, -99, and -100) were the most frequently detected BFRs and were found at concentrations consistent with those reported at other Arctic sites. Gas-particle distributions were influenced by temperature and correlations between gas-phase concentrations and temperature suggested that either volatilization from local sources or re-emission from secondary sources (that is, re-volatilization of BFRs that had migrated northwards from distant sources) was important for the lower-brominated BFRs during the warmer months. Source indicator analysis suggested no single dominant geographic source of BFRs while results from the flow-through samplers indicated that the field station itself was not a significant source of BFRs.

Runoff from manure-fertilized crop fields constitutes a significant source of natural estrogens (e.g., estradiol [17β-E2] and estrone [E1]) and synthetic estrogen mimics (e.g., zeranol [α-ZAL] and zearalanone [ZAN]) in the environment. However, processes such as sorption to and uptake by plants may inhibit the environmental mobility of hormonally active compounds. Sorption to dried root tissue was assessed in batch sorption tests, and resulting sorption isotherms were nonlinear at aqueous concentrations below 0.1 μM and linear above that limit. To evaluate the role of crop plants in the environmental fate of such compounds, we exposed hydroponic solutions containing 2 μM 17β-E2, E1, α-ZAL, or ZAN to maize seedlings. After 22 days of exposure, α-ZAL and ZAN concentrations decreased by more than 96%, and 17β-E2 and E1 were undetectable. The decrease in α-ZAL and ZAN concentrations in maize-exposed solutions was initially slow, but the observed uptake exceeded that predicted by sorption alone within 3 d. All four estrogens were detected in root tissues at concentrations up to 0.19 μmol g(-1), with concentrations peaking after 1-3 days of exposure. Only 17β-E2 and α-ZAL were detected in shoots, and maximum concentrations were measured after 2 days for 17β-E2 (0.02 μmol g(-1)) and 16 days for α-ZAL (0.8 nmol g(-1)). Concentrations measured in root and shoot tissues were 82% or less than those predicted by a partition-limited uptake model, which is attributed to transformation and possibly irreversible binding processes.

Prairie pothole lakes (PPLs) are critical hydrological and ecological components of central North America and represent one of the largest inland wetland systems on Earth. These lakes are located within an agricultural region, and many of them are subject to nonpoint-source pesticide pollution. Limited attention, however, has been paid to understanding the impact of PPL water chemistry on the fate and persistence of pesticides. In this study, the abiotic reductive transformation of seven dinitroaniline pesticides was investigated in PPL sediment porewaters containing naturally abundant levels of reduced sulfur species (i.e., bisulfide (HS(-)) and polysulfides (S(n)(2-))) and dissolved organic matter (DOM). Target dinitroanilines underwent rapid degradation in PPL porewaters and were transformed into corresponding amine products. While the largest fraction of the transformation could be attributed to reduced sulfur species, experimental evidence suggested that other reactive entities in PPL porewaters, such as DOM and mineral phases, might also affect the reaction rates of dinitroanilines. Results from this study highlight the importance of reductive transformation as an abiotic natural attenuation pathway for pesticides entering the PPL sedimentary environment.

The photolysis of caffeine was studied in solutions of fulvic acid isolated from Suwannee River, GA (SRFA) and Old Woman Creek Natural Estuarine Research Reserve, OH (OWCFA) with different chemical amendments (nitrate and iron). Caffeine degrades slowly by direct photolysis (>170 h in artificial sunlight), but we observed enhanced photodegradation in waters containing the fulvic acids. At higher initial concentrations (10 μM) the indirect photolysis of caffeine occurs predominantly through reaction with the hydroxyl radical (OH ) generated by irradiated fulvic acids. Both rate constant estimates based upon measured OH steady-state concentrations and quenching studies using isopropanol corroborate the importance of this pathway. Further, OH generated by irradiated nitrate at concentrations present in wastewater effluent plays an important role as a photosensitizer even in the presence of fulvic acids, while the photo-Fenton pathway does not at neutral or higher pH. At lower initial concentrations (0.1 μM) caffeine photolysis reactions proceed even more quickly in fulvic acid solutions and are influenced by both short- and long-lived reactive species. Studies conducted under suboxic conditions suggest that an oxygen dependent long-lived radical e.g., peroxyl radicals plays an important role in the degradation of caffeine at lower initial concentration.

Prairie pothole lakes (PPLs) are located within the extensively farmed Great Plains region of North America, and many are negatively impacted by nonpoint source pesticide pollution. To date, the environmental fate of pesticides in these lakes remains largely unknown. In this study, two PPLs in the Cottonwood Lake area of North Dakota were sampled, and transformations of four chloroacetanilide pesticides in sediment porewaters were examined. The reduced sulfur species in the porewaters, such as bisulfide (HS(-)) and polysulfides (S(n)(2-)), readily transformed the target pesticides into sulfur-substituted products. Although HS(-) and S(n)(2-) played a dominant role, other reactive constituents in PPL porewaters also contributed to the transformation. Results from this study revealed that abiotic reactions with reduced sulfur species could represent an important removal pathway for pesticides entering PPLs.

A major impediment to understanding the biology of microorganisms inhabiting Antarctic environments is the logistical constraint of conducting field work primarily during the summer season. However, organisms that persist throughout the year encounter severe environmental changes between seasons. In an attempt to bridge this gap, we collected ice core samples from Pony Lake in early November 2004 when the lake was frozen solid to its base, providing an archive for the biological and chemical processes that occurred during winter freezeup. The ice contained bacteria and virus-like particles, while flagellated algae and ciliates over-wintered in the form of inactive cysts and spores. Both bacteria and algae were metabolically active in the ice core melt water. Bacterial production ranged from 1.8 to 37.9 μg C L−1 day−1. Upon encountering favorable growth conditions in the melt water, primary production ranged from 51 to 931 μg C L−1 day−1. Because of the strong H2S odor and the presence of closely related anaerobic organisms assigned to Pony Lake bacterial 16S rRNA gene clones, we hypothesize that the microbial assemblage was strongly affected by oxygen gradients, which ultimately restricted the majority of phylotypes to distinct strata within the ice column. This study provides evidence that the microbial community over-winters in the ice column of Pony Lake and returns to a highly active metabolic state when spring melt is initiated.

Sulfadimethoxine (SDM) is an antibiotic often used in combination with ormetoprim to prevent the spread of disease in freshwater aquaculture. It is known to undergo photochemical degradation in natural sunlit surface waters, but the role of dissolved organic matter (DOM) in this process is poorly understood. Our results show that water from a eutrophic catfish pond at the Mississippi State University Delta Research and Extension Center facility in Stoneville, MS facilitates the rapid phototransformation of SDM. In contrast, water from a nearby stream (Deer Creek) whose DOM is derived from allochthonous precursors does not enhance SDM photodegradation. We attribute these disparate results to DOM composition, whereby dissolved organic matter originating from highly eutrophic water bodies is a better SDM photosensitizer. Experiments conducted concurrently using respective autochthonous (Pony Lake, Antarctica) and allochthonous (Suwannee River) derived fulvic acids corroborate these findings. Scavenging experiments and experiments conducted anoxically show that the main indirect photodegradation pathway occurs by triplet excited-state DOM oxidation. Finally, transformation products assayed by mass spectrometry reveal the same major SDM photoproducts in the presence and absence of dissolved organic matter.

Dissolved organic matter (DOM) chemical composition varies depending upon the source of its precursor materials. Results show that the indirect photodegradation rate coefficients for the compounds sulfadimethoxine (SDM) and triclocarban (TCC) differ depending on the source of fulvic acids used as DOM surrogates. For sulfadimethoxine, little to no enhanced photolysis occurred for the terrestrially derived Suwannee River fulvic acid, but the rate coefficients for triclocarban increased 28%. In contrast, a large photo-enhancement (48% for SDM and 45% for TCC) occurred in the presence of Pony Lake and Old Woman Creek fulvic acids, both of which are derived from predominantly autochthonous material. Conversely, the iron-promoted photodegradation of alachlor occurred more quickly in the presence of Suwannee River fulvic acid than another autochthonous fulvic acid isolated from Lake Fryxell, Antarctica. This pathway is dominated by reaction through hydroxyl radicals generated by the photolysis of the fulvic acids. Taken together, these data provide evidence that autochthonous fulvic acids are more reactive than allochthonous fulvic acids in promoting pathways involving triplet dissolved organic matter intermediates, whereas the latter are more reactive than the former in promoting degradation by some reactive oxygen species (ROS). Thus, more systematic studies are needed to determine the full extent of the linkage between fulvic acid composition and its ability to promote indirect photolytic processes and how the presence of other DOM fractions may affect these reactions.

The triplet state photochemistry of dissolved organic matter (DOM) isolated by XAD and C-18 chromatography and tangential flow ultrafiltration (TFUF) was investigated using 2,4,6 trimethylphenol (TMP) as a molecular probe. Water samples were taken from an Arctic seep adjacent the Oksrukuyik River (OKS) on the north slope of Alaska, USA, where DOM is derived primarily from allochthonous material and from a eutrophic midlatitude wetland, Old Woman Creek (OWC), in northern Ohio, USA, where the DOM is formed from both allochthonous and autochthonous precursors. DOM-mediated TMP photolysis occurred for all samples, but was significantly faster in the OWC isolates. The method used to isolate DOM also influenced TMP photoreactivity, whereby the C-18 and XAD isolated material were typically more reactive than ultrafiltered DOM. Analysis of the isolates by spectroscopy revealed that the materials isolated by chromatography were relatively enriched in aromatic constituents, while the TFUF fraction had the lowest aromaticity based on molar absorptivity at 280 nm. The fluorescence index values revealed differences between OKS and OWC, but no discernable trends were observed among isolates. This study shows that both the manner in which DOM is isolated and the composition of its precursors will influence its triplet state photoreactivity.