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Arsenic is a toxic metalloid with differential biological effects, depending on speciation and concentration. Trivalent arsenic (arsenite, AsIII) is more toxic at lower concentrations than the pentavalent form (arsenate, AsV). In E. coli, the proteins encoded by the arsRBC operon are the major arsenic detoxification mechanism. Our previous transcriptional analyses indicate broad changes in metal uptake and regulation upon arsenic exposure. Currently, it is not known how arsenic exposure impacts the cellular distribution of other metals. This study examines the metalloproteome of E. coli strains with and without the arsRBC operon in response to sublethal doses of AsIII and AsV. Size exclusion chromatography coupled with inductively coupled plasma mass spectrometry (SEC-ICPMS) was used to investigate the distribution of five metals (56Fe, 24Mg, 66Zn, 75As, and 63Cu) in proteins and protein complexes under native conditions. Parallel analysis by SEC-UV-Vis spectroscopy monitored the presence of protein cofactors. Together, these data reveal global changes in the metalloproteome, proteome, protein cofactors, and soluble intracellular metal pools in response to arsenic stress in E. coli. This work brings to light one outcome of metal exposure and suggests that metal toxicity on the cellular level arises from direct and indirect effects. 

Ecosystems that are coupled by reciprocal flows of energy and nutrient subsidies can be viewed as a single “meta‐ecosystem.” Despite these connections, the reciprocal flow of subsidies is greatly asymmetrical and seasonally pulsed. Here, we synthesize existing literature on stream–riparian meta‐ecosystems to quantify global patterns of the amount of subsidy consumption by organisms, known as “allochthony.” These resource flows are important since they can comprise a large portion of consumer diets, but can be disrupted by human modification of streams and riparian zones. Despite asymmetrical subsidy flows, we found stream and riparian consumer allochthony to be equivalent. Although both fish and stream invertebrates rely on seasonally pulsed allochthonous resources, we find allochthony varies seasonally only for fish, being nearly three times greater during the summer and fall than during the winter and spring. We also find that consumer allochthony varies with feeding traits for aquatic invertebrates, fish, and terrestrial arthropods, but not for terrestrial vertebrates. Finally, we find that allochthony varies by climate for aquatic invertebrates, being nearly twice as great in arid climates than in tropical climates, but not for fish. These findings are critical to understanding the consequences of global change, as ecosystem connections are being increasingly disrupted.

 

Several bacteria possess components of catabolic pathways for the synthetic polyester poly(ethylene terephthalate) (PET). These proceed by hydrolyzing the ester linkages of the polymer to its monomers, ethylene glycol and terephthalate (TPA), which are further converted into common metabolites. These pathways are crucial for genetically engineering microbes for PET upcycling, prompting interest in their fundamental biochemical and structural elucidation. Terephthalate dioxygenase (TPADO) and its cognate reductase make up a complex multimetalloenzyme system that dihydroxylates TPA, activating it for enzymatic decarboxylation to yield protocatechuic acid (PCA). Here, we report structural, biochemical, and bioinformatic analyses of TPADO. Together, these data illustrate the remarkable adaptation of TPADO to the TPA dianion as its preferred substrate, with small, protonatable ring 2-carbon substituents being among the few permitted substrate modifications. TPADO is a Rieske [2Fe2S] and mononuclear nonheme iron-dependent oxygenase (Rieske oxygenase) that shares low sequence similarity with most structurally characterized members of its family. Structural data show an α-helix–associated histidine side chain that rotates into an Fe (II)–coordinating position following binding of the substrate into an adjacent pocket. TPA interactions with side chains in this pocket were not conserved in homologs with different substrate preferences. The binding mode of the less symmetric 2-hydroxy-TPA substrate, the observation that PCA is its oxygenation product, and the close relationship of the TPADO α-subunit to that of anthranilate dioxygenase allowed us to propose a structure-based model for product formation. Future efforts to identify, evolve, or engineer TPADO variants with desirable properties will be enabled by the results described here. 

The latitudinal location of the east Pacific Ocean intertropical convergence zone (ITCZ) changes on time scales of days to weeks during boreal spring. This study focuses on tropical near-surface dynamics in the days leading up to the two most frequent types of ITCZ events, nITCZ (Northern Hemisphere) and dITCZ (double). There is a rapid daily evolution of dynamical features on top of a slower, weekly evolution that occurs leading up to and after nITCZ and dITCZ events. Zonally elongated bands of anomalous cross-equatorial flow and off-equatorial convergence rapidly intensify and peak 1 day before or the day of these ITCZ events, followed 1 or 2 days later by a peak in near-equatorial zonal wind anomalies. In addition, there is a wide region north of the southeast Pacific subtropical high where anomalous northwesterlies strengthen prior to nITCZ events and southeasterlies strengthen before dITCZ events. Anomalous zonal and meridional near-surface momentum budgets reveal that the terms associated with Ekman balance are of first-order importance preceding nITCZ events, but that the meridional momentum advective terms are just as important before dITCZ events. Variations in cross-equatorial flow are promoted by the meridional pressure gradient force (PGF) prior to nITCZ events and the meridional advection of meridional momentum in addition to the meridional PGF before dITCZ events. Meanwhile, variations in near-equatorial easterlies are driven by the zonal PGF and the Coriolis force preceding nITCZ events and the zonal PGF, the Coriolis force, and the meridional advection of zonal momentum before dITCZ events.

 

This study performs techno‐economic analysis and Monte Carlo simulations (MCS) to explore the effects that variations in biomass feedstock quality have on the economic feasibility of fast pyrolysis biorefineries using decentralized preprocessing sites (i.e., depots that produce pellets). Two biomass resources in the Southeastern United States, that is, pine residues and switchgrass, were examined as feedstocks. A scenario analysis was conducted for an array of different combinations, including different pellet ash control levels, feedstock blending ratios, different biorefinery capacities, and different biorefinery on‐stream capacities, followed by a comparison with the traditional centralized system. MCS results show that, with depot preprocessing, variations in the feedstock moisture and feedstock ash content can be significantly reduced compared with a traditional centralized system. For a biorefinery operating at 100% of its designed capacity, the minimum fuel selling price (MFSP) of the decentralized system is $3.97–$4.39 per gallon gasoline equivalent (GGE) based on the mean value across all scenarios, whereas the mean MFSP for the traditional centralized system was $3.79–$4.12/GGE. To understand the potential benefits of highly flowable pellets in decreasing biorefinery downtime due to feedstock handling and plugging problems, this study also compares the MFSP of the decentralized system at 90% of its designed capacity with a traditional system at 80%. The analysis illustrates that using low ash pellets mixed with switchgrass and pine residues generates a more competitive MFSP. Specifically, for a biorefinery designed for 2,000 oven dry metric ton per day, running a blended pellet made from 75% switchgrass and 25% pine residues with 2% ash level, and operating at 90% of designed capacity could make an MFSP between $4.49 and $4.71/GGE. In contrast, a traditional centralized biorefinery operating at 80% of designed capacity marks an MFSP between $4.72 and $5.28.