High-Resolution Nanoscale Solid-State Nuclear Magnetic Resonance Spectroscopy

We present a new method for high-resolution nanoscale magnetic resonance imaging (nano-MRI) that combines the high spin sensitivity of nanowire-based magnetic resonance detection with high spectral resolution nuclear magnetic resonance (NMR) spectroscopy. By applying NMR pulses designed using optimal control theory, we demonstrate a factor of $500$ reduction of the proton spin resonance linewidth in a $(50\text{-nm})^{\text{3}}$ volume of polystyrene and image proton spins in one dimension with a spatial resolution below $2~\text{nm}$.Comment: Main text: 8 pages, 6 figures; supplementary information: 10 pages, 10 figure

Photodegradation disproportionately impacts biodegradation of semi‐labile DOM in streams

Exposure of dissolved organic matter (DOM) to sunlight can increase or decrease the fraction that is biodegradable (BDOM), but conceptual models fail to explain this dichotomy. We investigated the effect of sunlight exposure on BDOM, addressing three knowledge gaps: (1) how fractions of DOM overlap in their susceptibility to degradation by sunlight and microbes, (2) how the net effect of sunlight on BDOM changes with photon dose, and (3) how rates of DOM photodegradation and biodegradation compare in a stream. Stream waters were exposed to sunlight, and then fed through bioreactors designed to separate labile and semi‐labile pools within BDOM. The net effects of photodegradation on DOM biodegradability, while generally positive, represented the balance between photochemical production and removal of BDOM that was mediated by photon dose. By using sunlight exposure times representative of sunlight exposures in a headwater stream and bioreactors colonized with natural communities and scaled to whole‐stream dynamics, we were able to relate our laboratory findings to the stream. The impact of sunlight exposure on rates of DOM biodegradation in streams was calculated using rates of light absorption by chromophoric DOM, apparent quantum yields for photomineralization and photochemical alteration of BDOM, and mass transfer coefficients for labile and semi‐labile DOM. Rates of photochemical alteration of labile DOM were an order of magnitude lower than rates of biodegradation of labile DOM, but for semi‐labile DOM, these rates were similar, suggesting that sunlight plays a substantial role in the fate of semi‐labile DOM in streams.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/153758/1/lno11244.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/153758/2/lno11244_am.pd

A Coupled Geochemical and Biogeochemical Approach to Characterize the Bioreactivity of Dissolved Organic Matter From a Headwater Stream

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31-45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1-0.5 or (2) low H/C of 0.5-1.0 spanning O/C 0.2-0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0-1.5, O/C 0.25-0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2-D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR-MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition

A coupled geochemical and biogeochemical approach to characterize the bioreactivity of dissolved organic matter from a headwater stream

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31–45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1–0.5 or (2) low H/C of 0.5–1.0 spanning O/C 0.2–0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0–1.5, O/C 0.25–0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2‐D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR‐MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition. Key Points Humic DOM is susceptible to microbial degradation along with peptide‐like DOM Labile DOM can be distinguished from recalcitrant DOM in van Krevelen space EEMs and FTICR‐MS chemically characterize bioreactive and recalcitrant DOMPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/108612/1/jgrg20256.pd

Surface exposure to sunlight stimulates CO 2 release from permafrost soil carbon in the Arctic

Recent climate change has increased arctic soil temperatures and thawed large areas of permafrost, allowing for microbial respiration of previously frozen C. Furthermore, soil destabilization from melting ice has caused an increase in thermokarst failures that expose buried C and release dissolved organic C (DOC) to surface waters. Once exposed, the fate of this C is unknown but will depend on its reactivity to sunlight and microbial attack, and the light available at the surface. In this study we manipulated water released from areas of thermokarst activity to show that newly exposed DOC is >40% more susceptible to microbial conversion to CO2 when exposed to UV light than when kept dark. When integrated over the water column of receiving rivers, this susceptibility translates to the light-stimulated bacterial activity being on average from 11% to 40% of the total areal activity in turbid versus DOC-colored rivers, respectively. The range of DOC lability to microbes seems to depend on prior light exposure, implying that sunlight may act as an amplification factor in the conversion of frozen C stores to C gases in the atmosphere

Experimental metatranscriptomics reveals the costs and benefits of dissolved organic matter photo‐alteration for freshwater microbes

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/156421/2/emi15121_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156421/1/emi15121.pd

Kinetics of superoxide reactions with dissolved organic matter in tropical Atlantic surface waters near Cape Verde (TENATSO)

The decay kinetics of superoxide (O2−) reacting with organic matter was examined in oligotrophic waters at, and nearby, the TENATSO ocean observatory adjacent to the Cape Verde archipelago. Superoxide is the short-lived primary photochemical product of colored dissolved organic matter (CDOM) photolysis and also reacts with CDOM or trace metals (Cu, Fe) to form H2O2. In the present work we focused our investigations on reactions between CDOM and superoxide. O2− decay kinetics experiments were performed by adding KO2 to diethylenetriaminepentaacetic acid (DTPA) amended seawater and utilizing an established chemiluminescence technique for the detection of O2− at nM levels. In Cape Verdean waters we found a significant reactivity of superoxide with CDOM with maximal rates adjacent to the chlorophyll maximum, presumably from production of new CDOM from bacteria/phytoplankton. This work highlights a poorly understood process which impacts on the biogeochemical cycling of CDOM and trace metals in the open ocean

Techno-Economic Analysis of Electrocoagulation on Water Reclamation and Bacterial/Viral Indicator Reductions of a High-Strength Organic Wastewater—Anaerobic Digestion Effluent

This study investigated the use of iron and aluminum and their combinations as electrodes to determine the technically sound and economically feasible electrochemical approach for the treatment of anaerobic digestion effluent. The results indicated that the use of iron as anode and cathode is the most suitable solution among different electrode combinations. The reduction of turbidity, total chemical oxygen demand, total phosphorus, total coliforms, Escherichia coli, Enterococci, and phages in the reclaimed water were 99%, 91%, 100%, 1.5 log, 1.7 log, 1.0 log, and 2.0 log, respectively. The economic assessment further concluded that the average treatment cost is $3 per 1000 L for a small-scale operation handling 3000 L wastewater/day. This study demonstrated that the electrocoagulation (EC) is a promising technique for the recovery and reclamation of water from anaerobic digestion effluent. Even though its energy consumption is higher and the nitrogen removal is insufficient compared to some conventional wastewater treatment technologies, there are several advantages of the EC treatment, such as short retention time, small footprint, no mixing, and gradual addition of coagulants. These features make EC technology applicable to be used alone or combined with other technologies for a wide range of wastewater treatment application

Reviews and syntheses: Effects of permafrost thaw on Arctic aquatic ecosystems

The Arctic is a water-rich region, with freshwater systems covering about 16 % of the northern permafrost landscape. Permafrost thaw creates new freshwater ecosystems, while at the same time modifying the existing lakes, streams, and rivers that are impacted by thaw. Here, we describe the current state of knowledge regarding how permafrost thaw affects lentic (still) and lotic (moving) systems, exploring the effects of both thermokarst (thawing and collapse of ice-rich permafrost) and deepening of the active layer (the surface soil layer that thaws and refreezes each year). Within thermokarst, we further differentiate between the effects of thermokarst in lowland areas vs. that on hillslopes. For almost all of the processes that we explore, the effects of thaw vary regionally, and between lake and stream systems. Much of this regional variation is caused by differences in ground ice content, topography, soil type, and permafrost coverage. Together, these modifying factors determine (i) the degree to which permafrost thaw manifests as thermokarst, (ii) whether thermokarst leads to slumping or the formation of thermokarst lakes, and (iii) the manner in which constituent delivery to freshwater systems is altered by thaw. Differences in thaw-enabled constituent delivery can be considerable, with these modifying factors determining, for example, the balance between delivery of particulate vs. dissolved constituents, and inorganic vs. organic materials. Changes in the composition of thaw-impacted waters, coupled with changes in lake morphology, can strongly affect the physical and optical properties of thermokarst lakes. The ecology of thaw-impacted lakes and streams is also likely to change; these systems have unique microbiological communities, and show differences in respiration, primary production, and food web structure that are largely driven by differences in sediment, dissolved organic matter, and nutrient delivery. The degree to which thaw enables the delivery of dissolved vs. particulate organic matter, coupled with the composition of that organic matter and the morphology and stratification characteristics of recipient systems will play an important role in determining the balance between the release of organic matter as greenhouse gases (CO2and CH4), its burial in sediments, and its loss downstream. The magnitude of thaw impacts on northern aquatic ecosystems is increasing, as is the prevalence of thaw-impacted lakes and streams. There is therefore an urgent need to quantify how permafrost thaw is affecting aquatic ecosystems across diverse Arctic landscapes, and the implications of this change for further climate warming.Additional co-authors: G. MacMillan, M. Rautio, K. M. Walter Anthony, and K. P. Wicklan