Biochemical and structural characterization of an aromatic ring-hydroxylating dioxygenase for terephthalic acid catabolism.

SignificanceMore than 400 million tons of plastic waste is produced each year, the overwhelming majority of which ends up in landfills. Bioconversion strategies aimed at plastics have emerged as important components of enabling a circular economy for synthetic plastics, especially those that exhibit chemically similar linkages to those found in nature, such as polyesters. The enzyme system described in this work is essential for mineralization of the xenobiotic components of poly(ethylene terephthalate) (PET) in the biosphere. Our description of its structure and substrate preferences lays the groundwork for in vivo or ex vivo engineering of this system for PET upcycling.

Global patterns of allochthony in stream-riparian meta-ecosystems.

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.

Flux Growth of an Intermetallic with Interstitial Fluorides via Decomposition of a Fluorocarbon.

La15(FeC6)4F2 was grown as large crystals by reacting iron in a La/Ni eutectic flux in the presence of decafluorobiphenyl (C12F10) which acts as both a carbon and fluoride source. This mild fluorinating technique enables the isolation of an intermetallic product containing fluoride interstitials, as opposed to forming ionic metal fluorides. The compound adopts a structure in the hexagonal crystal system with space group P6̅ which features FeC6 units composed of a central iron atom coordinated by three ethylenide units in a trigonal planar configuration. The structure is related to the previously reported La15(FeC6)4H, but with fluoride fully occupying the interstitial hydride positions, which induces partial occupancies and site splitting disorder in the adjacent layers of lanthanide ions. No supercell formation is observed.

Metal Flux Growth of Lanthanide Carbide Hydrides Using Anthracene.

Reactions of anthracene in Ln/T eutectic mixtures (Ln = La, Yb; T = Ni, Cu) have produced crystals of new complex lanthanide carbide hydride phases. The thermal decomposition of anthracene provides a source of both carbon and hydrogen. LaCHx forms in space group Pnma with unit cell parameters a = 7.2736(4) Å, b = 3.7218(2) Å, and c = 13.0727(7) Å. Yb2CHx forms in space group P-3m1 with unit cell parameters a = 3.5659(4) Å and c = 5.8000(8) Å, with a structure related to that of Ho2CF2. The presence of hydride in interstitial sites is supported by the formation of different compounds in the absence of hydrogen and by comparison to known hydride structures. 1H nuclear magnetic resonance (NMR) spectra collected on LaCHx show two unique hydride resonances, in agreement with the two available interstitial sites. Density of states calculations show that filling the tetrahedral sites in LaCHx with hydrogen increases metallic behavior, while adding hydrogen into the tetrahedral sites in Yb2CHx induces the formation of a band gap.

Top-down effects of repatriating bald eagles hinder jointly recovering competitors.

The recovery of piscivorous birds around the world is touted as one of the great conservation successes of the 21st century, but for some species, this success was short-lived. Bald eagles, ospreys and great blue herons began repatriating Voyageurs National Park, USA, in the mid-20th century. However, after 1990, only eagles continued their recovery, while osprey and heron recovery failed for unknown reasons. We aimed to evaluate whether top-down effects of bald eagles and bottom-up effects of inclement weather, habitat quality and fish resources contributed to the failed recovery of ospreys and herons in a protected area. We quantified the relative influence of top-down and bottom-up factors on nest colonization, persistence (i.e., nest reuse) and success for ospreys, and occurrence and size of heronries using 26 years (1986-2012) of spatially explicit monitoring data coupled with multi-response hierarchical models and Bayesian variable selection approaches. Bald eagles were previously shown to recover faster due to intensive nest protection and management. Increased numbers of eagles were associated with a reduction in the numbers of osprey nests, their nesting success and heronry size, while higher local densities of nesting eagles deterred heronries nearby. We found little evidence of bottom-up limitations on the failed recovery of herons and ospreys. We present a conservation conundrum: bald eagles are top predators and a flagship species of conservation that have benefited from intensive protection, but this likely hindered the recovery of ospreys and herons. Returning top predators, or rewilding, is widely promoted as a conservation strategy for top-down ecosystem recovery, but managing top predators in isolation of jointly recovering species can halt or reverse ecosystem recovery. Previous studies warn of the potential consequences of ignoring biotic interactions amongst recovering species, but we go further by quantifying how these interactions contributed to failed recoveries via impacts on the nesting demography of jointly recovering species. Multi-species management is paramount to realizing the ecosystem benefits of top predator recovery.

Employment Contracts: The Good, the Bad, and the Ugly.

Recent trends indicate that a greater number of orthopaedic surgeons who complete their residency and/or fellowship training are accepting employment positions at hospitals. Moreover, established orthopaedic surgeons with successful private practices have begun to consider whether aligning with hospitals and larger health systems can be effectively accomplished. A comprehensive evaluation of institution-based employment opportunities is essential for orthopaedic surgeons considering hospital-based employment. Surgeons should be aware of the healthcare, clinical, and administrative opportunities of private practice employment versus hospital-based employment before accepting a clinical position.

Bullying Victimization Type and Feeling Unsafe in Middle School.

Given their significance to school violence, this study quantifies the association between bullying victimization and perceptions of safety separately for victimization where the type is not specified versus victimization that is physical in nature. Generalized liner mixed modeling was employed with 5,138 sixth- to eighth-grade students in 24 schools who self-reported on their bullying victimization and perceptions of school safety on an anonymous survey in fall 2015. Results indicate a multiplicative interaction exists with regard to the odds of feeling unsafe at school among those who were bullied at all (odds ratio [ OR] = 3.1) compared to those who were bullied physically ( OR = 9.12). For school nurses who work with students with a variety of concerns and health issues, this research indicates that the use of bullying victimization as an outcome, proxy and/or predictor, requires inquiry into the type of bullying experienced to aid in the care and support received.

Human activities cause distinct dissolved organic matter composition across freshwater ecosystems.

Dissolved organic matter (DOM) composition in freshwater ecosystems is influenced by the interactions among physical, chemical, and biological processes that are controlled, at one level, by watershed landscape, hydrology, and their connections. Against this environmental template, humans may strongly influence DOM composition. Yet, we lack a comprehensive understanding of DOM composition variation across freshwater ecosystems differentially affected by human activity. Using optical properties, we described DOM variation across five ecosystem groups of the Laurentian Great Lakes region: large lakes, Kawartha Lakes, Experimental Lakes Area, urban stormwater ponds, and rivers (n = 184 sites). We determined how between ecosystem variation in DOM composition related to watershed size, land use and cover, water quality measures (conductivity, dissolved organic carbon (DOC), nutrient concentration, chlorophyll a), and human population density. The five freshwater ecosystem groups had distinctive DOM composition from each other. These significant differences were not explained completely through differences in watershed size nor spatial autocorrelation. Instead, multivariate partial least squares regression showed that DOM composition was related to differences in human impact across freshwater ecosystems. In particular, urban/developed watersheds with higher human population densities had a unique DOM composition with a clear anthropogenic influence that was distinct from DOM composition in natural land cover and/or agricultural watersheds. This nonagricultural, human developed impact on aquatic DOM was most evident through increased levels of a microbial, humic-like parallel factor analysis component (C6). Lotic and lentic ecosystems with low human population densities had DOM compositions more typical of clear water to humic-rich freshwater ecosystems but C6 was only present at trace to background levels. Consequently, humans are strongly altering the quality of DOM in waters nearby or flowing through highly populated areas, which may alter carbon cycles in anthropogenically disturbed ecosystems at broad scales.

Measuring spatial variation in secondary production and food quality using a common consumer approach in Lake Erie.

Lake Erie is a large lake straddling the border of the USA and Canada that has become increasingly eutrophic in recent years. Eutrophication is particularly focused in the shallow western basin. The western basin of Lake Erie is hydrodynamically similar to a large estuary, with riverine inputs from the Detroit and Maumee Rivers mixing together and creating gradients in chemical and physical conditions. This study was driven by two questions: (1) How does secondary production and food quality for consumers vary across this large mixing zone? and (2) Are there correlations between cyanobacterial abundance and secondary production or food quality for consumers? Measuring spatial and temporal variation in secondary production and food quality is difficult for a variety of logistical reasons, so here a common consumer approach was used. In a common consumer approach, individuals of a single species are raised under similar conditions until placed in the field across environmental gradients of interest. After some period of exposure, the response of that common consumer is measured to provide an index of spatial variation in conditions. Here, a freshwater mussel (Lampsilis siliquoidea) was deployed at 32 locations that spanned habitat types and a gradient in cyanobacterial abundance in the western basin of Lake Erie to measure spatial variation in growth (an index of secondary production) and fatty acid (FA) content (an index of food quality). We found secondary production was highest within the Maumee river mouth and lowest in the open waters of the lake. Mussel tissues in the Maumee river mouth also included more eicosapentaenoic and docosapentaenoic fatty acids (EPA and DPA, respectively), but fewer bacterial FAs, suggesting more algae at the base of the food web in the Maumee river mouth compared to open lake sites. The satellite-derived estimate of cyanobacterial abundance was not correlated to secondary production, but was positively related to EPA and DPA content in the mussels, suggesting more of these important FAs in locations with more cyanobacteria. These results suggest that growth of secondary consumers and the availability of important fatty acids in the western basin are centered on the Maumee river mouth.

Efficient Vocational Skills Training for People with Cognitive Disabilities: An Exploratory Study Comparing Computer-Assisted Instruction to One-on-One Tutoring.

BACKGROUND: This study compared the effectiveness of computer-assisted instruction to that of one-on-one tutoring for teaching people with mild and moderate cognitive disabilities when both training methods are designed to take account of the specific mental deficits most commonly found in cognitive disability populations. METHOD: Fifteen participants (age 22-71) received either computer-assisted instruction or one-on-one tutoring in three content domains that were of functional and daily relevance to them: behavioural limits, rights and responsibilities (two modules) and alphabetical sorting. Learning was assessed by means of a series of pretests and four learning cycle post-tests. Both instructional conditions maintained time-on-task and teaching material equivalence, and both incorporated a set of best-practices and empirically supported teaching techniques designed to address attentional deficits, stimulus processing inefficiencies and cognitive load limitations. RESULTS: Strong evidence of learning was found in both instructional method conditions. Moreover, in all content domains the two methods yielded approximately equivalent rates of learning and learning attainment. CONCLUSIONS: These findings offer tentative evidence that a repetitive, computer-assisted training program can produce learning outcomes in people with mild and moderate cognitive disabilities that are comparable to those achieved by high-quality one-on-one tutoring.

Can mercury in fish be reduced by water level management? Evaluating the effects of water level fluctuation on mercury accumulation in yellow perch (Perca flavescens).

Mercury (Hg) contamination of fisheries is a major concern for resource managers of many temperate lakes. Anthropogenic Hg contamination is largely derived from atmospheric deposition within a lake's watershed, but its incorporation into the food web is facilitated by bacterial activity in sediments. Temporal variation in Hg content of fish (young-of-year yellow perch) in the regulated lakes of the Rainy-Namakan complex (on the border of the United States and Canada) has been linked to water level (WL) fluctuations, presumably through variation in sediment inundation. As a result, Hg contamination of fish has been linked to international regulations of WL fluctuation. Here we assess the relationship between WL fluctuations and fish Hg content using a 10-year dataset covering six lakes. Within-year WL rise did not appear in strongly supported models of fish Hg, but year-to-year variation in maximum water levels (∆maxWL) was positively associated with fish Hg content. This WL effect varied in magnitude among lakes: In Crane Lake, a 1 m increase in ∆maxWL from the previous year was associated with a 108 ng increase in fish Hg content (per gram wet weight), while the same WL change in Kabetogama was associated with only a 5 ng increase in fish Hg content. In half the lakes sampled here, effect sizes could not be distinguished from zero. Given the persistent and wide-ranging extent of Hg contamination and the large number of regulated waterways, future research is needed to identify the conditions in which WL fluctuations influence fish Hg content.

Homologous acetone carboxylases select Fe(II) or Mn(II) as the catalytic cofactor.

Acetone carboxylases (ACs) catalyze the metal- and ATP-dependent conversion of acetone and bicarbonate to form acetoacetate. Interestingly, two homologous ACs that have been biochemically characterized have been reported to have different metal complements, implicating different metal dependencies in catalysis. ACs from proteobacteria Xanthobacter autotrophicus and Aromatoleum aromaticum share 68% sequence identity but have been proposed to have different catalytic metals. In this work, the two ACs were expressed under the same conditions in Escherichia coli and were subjected to parallel chelation and reconstitution experiments with Mn(II) or Fe(II). Electron paramagnetic and Mössbauer spectroscopies identified signatures, respectively, of Mn(II) or Fe(II) bound at the active site. These experiments showed that the respective ACs, without the assistance of chaperones, second metal sites, or post-translational modifications facilitate correct metal incorporation, and despite the expected thermodynamic preference for Fe(II), each preferred a distinct metal. Catalysis was likewise associated uniquely with the cognate metal, though either could potentially serve the proposed Lewis acidic role. Subtle differences in the protein structure are implicated in serving as a selectivity filter for Mn(II) or Fe(II).IMPORTANCEThe Irving-Williams series refers to the predicted stabilities of transition metal complexes where the observed general stability for divalent first-row transition metal complexes increase across the row. Acetone carboxylases (ACs) use a coordinated divalent metal at their active site in the catalytic conversion of bicarbonate and acetone to form acetoacetate. Highly homologous ACs discriminate among different divalent metals at their active sites such that variations of the enzyme prefer Mn(II) over Fe(II), defying Irving-Williams-predicted behavior. Defining the determinants that promote metal discrimination within the first-row transition metals is of broad fundamental importance in understanding metal-mediated catalysis and metal catalyst design.

Arsenic Exposure Causes Global Changes in the Metalloproteome of Escherichia coli.

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.

Dissolved organic matter transformations in a freshwater rivermouth.

River-to-lake transitional areas are biogeochemically active ecosystems that can alter the amount and composition of dissolved organic matter (DOM) as it moves through the aquatic continuum. However, few studies have directly measured carbon processing and assessed the carbon budget of freshwater rivermouths. We compiled measurements of dissolved organic carbon (DOC) and DOM in several water column (light and dark) and sediment incubation experiments conducted in the mouth of the Fox river (Fox rivermouth) upstream from Green Bay, Lake Michigan. Despite variation in the direction of DOC fluxes from sediments, we found that the Fox rivermouth was a net sink of DOC where water column DOC mineralization outweighed the release of DOC from sediments at the rivermouth scale. Although we found DOM composition also changed during our experiments, alterations in DOM optical properties were largely independent of the direction of sediment DOC fluxes. We found a consistent decrease in humic-like and fulvic-like terrestrial DOM and a consistent increase in the overall microbial composition of rivermouth DOM during our incubations. Moreover, greater ambient total dissolved phosphorus concentrations were positively associated with the consumption of terrestrial humic-like, microbial protein-like, and more recently derived DOM but had no effect on bulk DOC in the water column. Unexplained variation indicates that other environmental controls and water column processes affect the processing of DOM in this rivermouth. Nonetheless, the Fox rivermouth appears capable of substantial DOM transformation with implications for the composition of DOM entering Lake Michigan. Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-022-01000-z.

Biofouling of a unionid mussel by dreissenid mussels in nearshore zones of the Great Lakes.

In North America, native unionid mussels are imperiled due to factors such as habitat degradation, pollution, and invasive species. One of the most substantial threats is that posed by dreissenid mussels, which are invasive mussels that attach to hard substrates including unionid shells and can restrict movement and feeding of unionids. This dreissenid mussel biofouling of unionids varies spatially in large ecosystems, such as the Great Lakes, with some areas having low enough biofouling to form effective refugia where unionid mussels might persist. Here, we measured biofouling on mussels suspended in cages over the growing season (generally first week in June to last week of August) over 3 years in nearshore areas in Lake Erie (2014-2016), Lake Michigan (Grand Traverse Bay, 2015 and Green Bay, 2016), and Lake Huron (2015). Biofouling varied substantially by years within Lake Erie, with increasingly higher biofouling rates each year. Although dreissenid mussels are present throughout these lakes, we observed very low biofouling in Grand Traverse Bay (Lake Michigan) and Saginaw Bay (Lake Huron), with no dreissenid mussels in 8 of 9 sites across these two bays. Sampling in the rivermouth of the Fox River (Wisconsin) and the Maumee River (Ohio) both showed very high biofouling in areas adjacent to the outlet of these tributaries into Green Bay and Maumee Bay (Lake Erie), respectively. These watersheds are dominated by agriculture, and we would expect high growth of primary producers (i.e., mussel food) and primary consumers (unionids and zebra mussels) in these areas compared to the other sampled bays or the open waters of the Great Lakes.

Health disparity: time delay in the treatment of breast cancer in Louisiana.

Previous studies have suggested that breast cancer patients with a delay of three months or more in initiating radiotherapy after breast conservative surgery, have increased recurrence and lower survival than those without treatment delay. In this study, the inequalities in receiving radiation on time after surgery were identified in five areas--patient's age at diagnosis, race, size of the facility where the patient received treatment, teaching status of the facilities and geographical location where the patient received treatment. All patients studied were female patients. Women younger than 50 years of age, of the black race, receiving treatment in a teaching hospital, and who were treated by surgeons in southeast and central Louisiana were more likely to experience delay in receiving radiotherapy after breast conservative surgery than their counterparts. Patient's insurance status, marital status and SES did not have any influence on treatment delay. Also, the surgeon's practice age at diagnosis, the surgeon's medical school, facility ownership status and Commission on Cancer approval status did not show significant effect.

Transgenerational effects of poor elemental food quality on Daphnia magna.

Environmental effects on parents can strongly affect the phenotype of their offspring, which alters the heritability of traits and the offspring's responses to the environment. We examined whether P limitation of the aquatic invertebrate, Daphnia magna, alters the responses of its offspring to inadequate P nutrition. Mother Daphnia consuming P-poor algal food produced smaller neonates having lower body P content compared to control (P-rich) mothers. These offspring from P-stressed mothers, when fed P-rich food, grew faster and reproduced on the same schedule as those from P-sufficient mothers. In contrast, offspring from P-stressed mothers, when fed P-poor food, grew more slowly and had delayed reproduction compared to their sisters born to control mothers. There was also weak evidence that daughters from P-stressed mothers are more susceptible to infection by the virulent bacterium, Pasteuria ramosa. Our results show that P stress is not only transferred across generations, but also that its effect on the offspring generation varies depending upon the quality of their own environment. Maternal P nutrition can thus determine the nature of offspring responses to food P content and potentially obfuscates relationships between the performance of offspring and their own nutrition. Given that food quality can be highly variable within and among natural environments, our results demonstrate that maternal effects should be included as an additional dimension into studies of how elemental nutrition affects the physiology, ecology, and evolution of animal consumers.

Health policy and exercise: a brief BRFSS study and recommendations.

The Behavioral Risk Factor Surveillance Survey is used to compare three predictors of self-rated health, specifically exercise, tobacco smoking, and a diagnosis of diabetes (a proxy for obesity). Exercise is found to be the best predictor, and the remainder of the article discusses the role of exercise in disease prevention and the all-important concept of exercise adherence. Government policy in the future needs to promote exercise adherence in a more rigorous way, because it is a key to both individual and societal health. Exercise habits need to be instilled from youth, and physical education requirements in school need to be re-established at all levels through high school. Adults also need encouragement with better neighborhood planning of exercise trails for walking and biking, as well as planned community activities to encourage fitness through one's lifetime. The article concludes with six recommendations for formal government action to encourage exercise adherence.