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Browsing College of Agriculture and Life Sciences (CALS) by Subject "03 Chemical Sciences"
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- The electronic structure of FeV-cofactor in vanadium-dependent nitrogenaseYang, Zhi-Yong; Jimenez-Vicente, Emilio; Kallas, Hayden; Lukoyanov, Dmitriy A.; Yang, Hao; Del Campo, Julia S. Martin; Dean, Dennis R.; Hoffman, Brian M.; Seefeldt, Lance C. (Royal Society of Chemistry, 2021-03-29)The electronic structure of the active-site metal cofactor (FeV-cofactor) of resting-state V-dependent nitrogenase has been an open question, with earlier studies indicating that it exhibits a broad S = 3/2 EPR signal (Kramers state) having g values of ∼4.3 and 3.8, along with suggestions that it contains metal-ions with valencies [1V3+, 3Fe3+, 4Fe2+]. In the present work, genetic, biochemical, and spectroscopic approaches were combined to reveal that the EPR signals previously assigned to FeV-cofactor do not correlate with active VFe-protein, and thus cannot arise from the resting-state of catalytically relevant FeV-cofactor. It, instead, appears resting-state FeV-cofactor is either diamagnetic, S = 0, or non-Kramers, integer-spin (S = 1, 2 etc.). When VFe-protein is freeze-trapped during high-flux turnover with its natural electron-donating partner Fe protein, conditions which populate reduced states of the FeV-cofactor, a new rhombic S = 1/2 EPR signal from such a reduced state is observed, with g = [2.18, 2.12, 2.09] and showing well-defined 51V (I = 7/2) hyperfine splitting, aiso = 110 MHz. These findings indicate a different assignment for the electronic structure of the resting state of FeV-cofactor: S = 0 (or integer-spin non-Kramers state) with metal-ion valencies, [1V3+, 4Fe3+, 3Fe2+]. Our findings suggest that the V3+ does not change valency throughout the catalytic cycle.
- Establishment of the predator Laricobius nigrinus, introduced as a biological control agent for hemlock woolly adelgid in Virginia, USAJubb, Carrie S.; McAvoy, Thomas J.; Stanley, Kari E.; Heminger, Ariel R.; Salom, Scott M. (Springer, 2021-01-05)Laricobius nigrinus Fender (Coleoptera: Derodontidae), a predatory beetle native to western North America, has been released since 2003 for management of hemlock woolly adelgid (HWA), Adelges tsugae Annand (Hemiptera: Adelgidae), a non-native pest killing hemlocks in eastern North America. Over 420,000 L. nigrinus have been released in the eastern USA from field and lab-reared sources, 14,000 of which were deployed in the Commonwealth of Virginia, USA. In order to determine the establishment rates of L. nigrinus in Virginia, surveys were conducted in 2017 and 2018 at all release sites within this state. During the study, stand-level HWA densities were estimated, and hemlock tree health and predator–prey ratios were quantified. The identification of Laricobius spp. recoveries were made using microsatellite analysis. During the period of the study, L. nigrinus were found to have established at 82% of Virginia release sites and were the primary species recovered (80%). Both Laricobius rubidus (18%) and hybrids (2%) were also recovered. Stand-level HWA densities varied greatly over sites and years but showed a general decline in year two of the study. Establishment at such a high percentage of release sites suggests that the climate in Virginia is suitable for the predator and the insect is adaptable to the wide variety of site conditions where hemlocks typically grow.
- Macroinvertebrate sensitivity thresholds for sediment in Virginia streamsGovenor, Heather; Krometis, Leigh-Anne H.; Willis, Lawrence; Angermeier, Paul L.; Hession, W. Cully (2019-01)Sediment is the most commonly identified pollutant associated with macroinvertebrate community impairments in freshwater streams nationwide. Management of this physical stressor is complicated by the multiple measures of sediment available (e.g., suspended, dissolved, bedded) and the variability in natural "healthy" sediment loadings across ecoregions. Here we examine the relative importance of 9 sediment parameters on macroinvertebrate community health as measured by the Virginia Stream Condition Index (VSCI) across 5 ecoregions. In combination, sediment parameters explained 27.4% of variance in the VSCI in a multiregion data set and from 20.2% to 76.4% of variance for individual ecoregions. Bedded sediment parameters had a stronger influence on VSCI than did dissolved or suspended parameters in the multiregion assessment. However, assessments of individual ecoregions revealed conductivity had a key influence on VSCI in the Central Appalachian, Northern Piedmont and Piedmont ecoregions. In no case was a single sediment parameter sufficient to predict VSCI scores or individual biological metrics. Given the identification of embeddedness and conductivity as key parameters for predicting biological condition, we developed family-level sensitivity thresholds for these parameters, based on extirpation. Resulting thresholds for embeddedness were 68% for combined ecoregions, 65% for the Mountain bioregion (composed of Central Appalachian, Ridge and Valley, and Blue Ridge ecoregions), and 88% for the Piedmont bioregion (composed of Northern Piedmont and Piedmont ecoregions). Thresholds for conductivity were 366 μS/cm for combined ecoregions, 391 μS/cm for the Mountain bioregion, and 136 μS/cm for the Piedmont bioregion. These thresholds may help water quality professionals identify impaired and at-risk waters designated to support aquatic life and develop regional strategies to manage sediment-impaired streams. Inclusion of embeddedness as a restoration endpoint may be warranted; this could be facilitated by application of more quantitative, less time-intensive measurement approaches. We encourage refinement of thresholds as additional data and genus-based metrics become available. Integr Environ Assess Manag 2019;15:77-92. Published 2018. This article has been contributed to by US Government employees and their work is in the public domain in the USA.