Identifying potential provenances for climate-change adaptation using spatially variable coefficient models.

BACKGROUND: Selection of climate-change adapted ecotypes of commercially valuable species to date relies on DNA-assisted screening followed by growth trials. For trees, such trials can take decades, hence any approach that supports focussing on a likely set of candidates may save time and money. We use a non-stationary statistical analysis with spatially varying coefficients to identify ecotypes that indicate first regions of similarly adapted varieties of Douglas-fir (Pseudotsuga menziesii (Mirbel) Franco) in North America. For over 70,000 plot-level presence-absences, spatial differences in the survival response to climatic conditions are identified. RESULTS: The spatially-variable coefficient model fits the data substantially better than a stationary, i.e. constant-effect analysis (as measured by AIC to account for differences in model complexity). Also, clustering the model terms identifies several potential ecotypes that could not be derived from clustering climatic conditions itself. Comparing these six identified ecotypes to known genetically diverging regions shows some congruence, as well as some mismatches. However, comparing ecotypes among each other, we find clear differences in their climate niches. CONCLUSION: While our approach is data-demanding and computationally expensive, with the increasing availability of data on species distributions this may be a useful first screening step during the search for climate-change adapted varieties. With our unsupervised learning approach being explorative, finely resolved genotypic data would be helpful to improve its quantitative validation.

Mule deer fawn recruitment dynamics in an energy disturbed landscape.

Wildlife population dynamics are modulated by abiotic and biotic factors, typically climate, resource availability, density-dependent effects, and predator-prey interactions. Understanding whether and how human-caused disturbances shape these ecological processes is helpful for the conservation and management of wildlife and their habitats within increasingly human-dominated landscapes. However, many jurisdictions lack either long-term longitudinal data on wildlife populations or measures of the interplay between human-mediated disturbance, climate, and predator density. Here, we use a 50-year time series (1962-2012) on mule deer (Odocoileus hemionus) demographics, seasonal weather, predator density, and oil and gas development patterns from the North Dakota Badlands, USA, to investigate long-term effects of landscape-level disturbance on mule deer fawn fall recruitment, which has declined precipitously over the last number of decades. Mule deer fawn fall recruitment in this study represents the number of fawns per female (fawn:female ratio) that survive through the summer to October. We used this fawn recruitment index to evaluate the composite effects of interannual extreme weather conditions, energy development, and predator density. We found that density-dependent effects and harsh seasonal weather were the main drivers of fawn fall recruitment in the North Dakota Badlands. These effects were further shaped by the interaction between harsh seasonal weather and predator density (i.e., lower fawn fall recruitment when harsh weather was combined with higher predator density). Additionally, we found that fawn fall recruitment was modulated by interactions between seasonal weather and energy development (i.e., lower fawn fall recruitment when harsh weather was combined with higher density of active oil and gas wells). Interestingly, we found that the combined effect of predator density and energy development was not interactive but rather additive. Our analysis demonstrates how energy development may modulate fluctuations in mule deer fawn fall recruitment concurrent with biotic (density-dependency, habitat, predation, woody vegetation encroachment) and abiotic (harsh seasonal weather) drivers. Density-dependent patterns emerge, presumably due to limited quality habitat, being the primary factor influencing fall fawn recruitment in mule deer. Secondarily, stochastic weather events periodically cause dramatic declines in recruitment. And finally, the additive effects of human disturbance and predation can induce fluctuations in fawn fall recruitment. Here we make the case for using long-term datasets for setting long-term wildlife management goals that decision makers and the public can understand and support.

An integrated knowledge synthesis of regional ambient monitoring in Canada's oil sands.

The desire to document and understand the cumulative implications of oil sands (OS) development in the ambient environment of northeastern Alberta has motivated increased investment and release of information in the past decade. Here, we summarize the knowledge presented in the theme-based review papers in this special series, including air, surface water, terrestrial biology, and Indigenous community-based monitoring in order to (1) consolidate knowledge gained to date, (2) highlight key commonalities and gaps, and (3) leverage this knowledge to assess the state of integration in environmental monitoring efforts in the OS region and suggest next steps. Among air, water, and land studies, the individual reviews identified a clear focus on describing stressors, including primarily (1) contaminant emission, transport, transformation, deposition, and exposure, and (2) landscape disturbance. These emphases are generally partitioned by theme; air and water studies focus heavily on chemical stressors, whereas terrestrial monitoring focuses on biological change and landscape disturbance. Causal attribution is often stated as a high priority objective across all themes. However, studies often rely on spatial proximity to attribute cause to industrial activity, leaving causal attribution potentially confounded by spatial covariance of both OS- and non-OS-related stressors in the region, and by the complexity of interacting pathways between sources of environmental change and ecological receptors. Geospatial and modeling approaches are common across themes and may represent clear integration opportunities, particularly to help inform investigation-of-cause, but are not a replacement for robust field monitoring designs. Cumulative effects assessment remains a common focus of regional monitoring, but is limited in the peer-reviewed literature, potentially reflecting a lack of integration among monitoring efforts beyond narrow integrated interpretations of results. Addressing this requires greater emphasis on a priori integrated data collection and integrated analyses focused on the main residual exposure pathways, such as atmospheric deposition. Integr Environ Assess Manag 2022;18:428-441. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

A synthetic review of terrestrial biological research from the Alberta oil sands region: 10 years of published literature.

In the past decade, a large volume of peer-reviewed papers has examined the potential impacts of oil and gas resource extraction in the Canadian oil sands (OS). A large proportion focuses on terrestrial biology: wildlife, birds, and vegetation. We provide a qualitative synthesis of the condition of the environment in the oil sands region (OSR) from 2009 to 2020 to identify gaps and progress cumulative effects assessments. Our objectives were to (1) qualitatively synthesize and critically review knowledge from the OSR; (2) identify consistent trends and generalizable conclusions; and (3) pinpoint gaps in need of greater monitoring or research effort. We visualize knowledge and terrestrial monitoring foci by allocating papers to a conceptual model for the OS. Despite a recent increase in publications, focus has remained concentrated on a few key stressors, especially landscape disturbance, and a few taxa of interest. Stressor and response monitoring is well represented, but direct monitoring of pathways (linkages between stressors and responses) is limited. Important knowledge gaps include understanding effects at multiple spatial scales, mammal health effects monitoring, focused monitoring of local resources important to Indigenous communities, and geospatial coverage and availability, including higher attribute resolution in human footprint, comprehensive land cover mapping, and up-to-date LiDAR coverage. Causal attribution based on spatial proximity to operations or spatial orientation of monitoring in the region is common but may be limited in the strength of inference that it provides. Integr Environ Assess Manag 2022;18:388-406. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Climatic, topographic, and anthropogenic factors determine connectivity between current and future climate analogs in North America.

As climatic conditions shift in coming decades, persistence of many populations will depend on their ability to colonize habitat newly suitable for their climatic requirements. Opportunities for such range shifts may be limited unless areas that facilitate dispersal under climate change are identified and protected from land uses that impede movement. While many climate adaptation strategies focus on identifying refugia, this study is the first to characterize areas which merit protection for their role in promoting climate connectivity at a continental extent. We identified climate connectivity areas across North America by delineating paths between current climate types and their future analogs that avoided nonanalogous climates, and used centrality metrics to rank the contribution of each location to facilitating dispersal across the landscape. The distribution of connectivity areas was influenced by climatic and topographic factors at multiple spatial scales. Results were robust to uncertainty in the magnitude of future climate change arising from differing emissions scenarios and general circulation models, but sensitive to analysis extent and assumptions concerning dispersal behavior and maximum dispersal distance. Paths were funneled along north-south trending passes and valley systems and away from areas of novel and disappearing climates. Climate connectivity areas, where many potential dispersal paths overlapped, were distinct from refugia and thus poorly captured by many existing conservation strategies. Existing protected areas with high connectivity values were found in southern Mexico, the southwestern US, and western and arctic Canada and Alaska. Ecoregions within the Isthmus of Tehuantepec, Great Plains, eastern temperate forests, high Arctic, and western Canadian Cordillera hold important climate connectivity areas which merit increased conservation focus due to anthropogenic pressures or current low levels of protection. Our coarse-filter climate-type-based results complement and contextualize species-specific analyses and add a missing dimension to climate adaptation planning by identifying landscape features which promote connectivity among refugia.

Distribution and protection of climatic refugia in North America.

As evidenced by past climatic refugia, locations projected to harbor remnants of present-day climates may serve as critical refugia for current biodiversity in the face of modern climate change. We mapped potential climatic refugia in the future across North America, defined as locations with increasingly rare climatic conditions. We identified these locations by tracking projected changes in the size and distribution of climate analogs over time. We used biologically derived thresholds to define analogs and tested the impacts of dispersal limitation with 4 distances to limit analog searches. We identified at most 12% of North America as potential climatic refugia. Refugia extent varied depending on the analog threshold, dispersal distance, and climate projection. However, in all cases refugia were concentrated at high elevations and in topographically complex regions. Refugia identified using different climate projections were largely nested, suggesting that identified refugia were relatively robust to climate-projection selection. Existing conservation areas cover approximately 10% of North America and yet protected up to 25% of identified refugia, indicating that protected areas disproportionately include refugia. Refugia located at lower latitudes (≤40°N) and slightly lower elevations (approximately 2500 m) were more likely to be unprotected. Based on our results, a 23% expansion of the protected-area network would be sufficient to protect the refugia present under all 3 climate projections we explored. We believe these refugia are high conservation priorities due to their potential to harbor rare species in the future. However, these locations are simultaneously highly vulnerable to climate change over the long term. These refugia contracted substantially between the 2050s and the 2080s, which supports the idea that the pace of climate change will strongly determine the availability and effectiveness of refugia for protecting today's biodiversity.

Post-glacial biogeography of trembling aspen inferred from habitat models and genetic variance in quantitative traits.

Using species distribution models and information on genetic structure and within-population variance observed in a series of common garden trials, we reconstructed a historical biogeography of trembling aspen in North America. We used an ensemble classifier modelling approach (RandomForest) to reconstruct palaeoclimatic habitat for the periods 21,000, 14,000, 11,000 and 6,000 years before present. Genetic structure and diversity in quantitative traits was evaluated in common garden trials with 43 aspen collections ranging from Minnesota to northern British Columbia. Our main goals were to examine potential recolonisation routes for aspen from southwestern, eastern and Beringian glacial refugia. We further examined if any refugium had stable habitat conditions where aspen clones may have survived multiple glaciations. Our palaeoclimatic habitat reconstructions indicate that aspen may have recolonised boreal Canada and Alaska from refugia in the eastern United States, with separate southwestern refugia for the Rocky Mountain regions. This is further supported by a southeast to northwest gradient of decreasing genetic variance in quantitative traits, a likely result of repeated founder effects. Stable habitat where aspen clones may have survived multiple glaciations was predicted in Mexico and the eastern United States, but not in the west where some of the largest aspen clones have been documented.

Scale-dependent complementarity of climatic velocity and environmental diversity for identifying priority areas for conservation under climate change.

As most regions of the earth transition to altered climatic conditions, new methods are needed to identify refugia and other areas whose conservation would facilitate persistence of biodiversity under climate change. We compared several common approaches to conservation planning focused on climate resilience over a broad range of ecological settings across North America and evaluated how commonalities in the priority areas identified by different methods varied with regional context and spatial scale. Our results indicate that priority areas based on different environmental diversity metrics differed substantially from each other and from priorities based on spatiotemporal metrics such as climatic velocity. Refugia identified by diversity or velocity metrics were not strongly associated with the current protected area system, suggesting the need for additional conservation measures including protection of refugia. Despite the inherent uncertainties in predicting future climate, we found that variation among climatic velocities derived from different general circulation models and emissions pathways was less than the variation among the suite of environmental diversity metrics. To address uncertainty created by this variation, planners can combine priorities identified by alternative metrics at a single resolution and downweight areas of high variation between metrics. Alternately, coarse-resolution velocity metrics can be combined with fine-resolution diversity metrics in order to leverage the respective strengths of the two groups of metrics as tools for identification of potential macro- and microrefugia that in combination maximize both transient and long-term resilience to climate change. Planners should compare and integrate approaches that span a range of model complexity and spatial scale to match the range of ecological and physical processes influencing persistence of biodiversity and identify a conservation network resilient to threats operating at multiple scales.

Biotic and Climatic Velocity Identify Contrasting Areas of Vulnerability to Climate Change.

Metrics that synthesize the complex effects of climate change are essential tools for mapping future threats to biodiversity and predicting which species are likely to adapt in place to new climatic conditions, disperse and establish in areas with newly suitable climate, or face the prospect of extirpation. The most commonly used of such metrics is the velocity of climate change, which estimates the speed at which species must migrate over the earth's surface to maintain constant climatic conditions. However, "analog-based" velocities, which represent the actual distance to where analogous climates will be found in the future, may provide contrasting results to the more common form of velocity based on local climate gradients. Additionally, whereas climatic velocity reflects the exposure of organisms to climate change, resultant biotic effects are dependent on the sensitivity of individual species as reflected in part by their climatic niche width. This has motivated development of biotic velocity, a metric which uses data on projected species range shifts to estimate the velocity at which species must move to track their climatic niche. We calculated climatic and biotic velocity for the Western Hemisphere for 1961-2100, and applied the results to example ecological and conservation planning questions, to demonstrate the potential of such analog-based metrics to provide information on broad-scale patterns of exposure and sensitivity. Geographic patterns of biotic velocity for 2954 species of birds, mammals, and amphibians differed from climatic velocity in north temperate and boreal regions. However, both biotic and climatic velocities were greatest at low latitudes, implying that threats to equatorial species arise from both the future magnitude of climatic velocities and the narrow climatic tolerances of species in these regions, which currently experience low seasonal and interannual climatic variability. Biotic and climatic velocity, by approximating lower and upper bounds on migration rates, can inform conservation of species and locally-adapted populations, respectively, and in combination with backward velocity, a function of distance to a source of colonizers adapted to a site's future climate, can facilitate conservation of diversity at multiple scales in the face of climate change.

Glacial refugia and modern genetic diversity of 22 western North American tree species.

North American tree species, subspecies and genetic varieties have primarily evolved in a landscape of extensive continental ice and restricted temperate climate environments. Here, we reconstruct the refugial history of western North American trees since the last glacial maximum using species distribution models, validated against 3571 palaeoecological records. We investigate how modern subspecies structure and genetic diversity corresponds to modelled glacial refugia, based on a meta-analysis of allelic richness and expected heterozygosity for 473 populations of 22 tree species. We find that species with strong genetic differentiation into subspecies had widespread and large glacial refugia, whereas species with restricted refugia show no differentiation among populations and little genetic diversity, despite being common over a wide range of environments today. In addition, a strong relationship between allelic richness and the size of modelled glacial refugia (r(2) = 0.55) suggest that population bottlenecks during glacial periods had a pronounced effect on the presence of rare alleles.

Velocity of climate change algorithms for guiding conservation and management.

The velocity of climate change is an elegant analytical concept that can be used to evaluate the exposure of organisms to climate change. In essence, one divides the rate of climate change by the rate of spatial climate variability to obtain a speed at which species must migrate over the surface of the earth to maintain constant climate conditions. However, to apply the algorithm for conservation and management purposes, additional information is needed to improve realism at local scales. For example, destination information is needed to ensure that vectors describing speed and direction of required migration do not point toward a climatic cul-de-sac by pointing beyond mountain tops. Here, we present an analytical approach that conforms to standard velocity algorithms if climate equivalents are nearby. Otherwise, the algorithm extends the search for climate refugia, which can be expanded to search for multivariate climate matches. With source and destination information available, forward and backward velocities can be calculated allowing useful inferences about conservation of species (present-to-future velocities) and management of species populations (future-to-present velocities).

Idiosyncratic responses of grizzly bear habitat to climate change based on projected food resource changes.

Climate change vulnerability assessments for species of conservation concern often use species distribution and ecological niche modeling to project changes in habitat. One of many assumptions of these approaches is that food web dependencies are consistent in time and environmental space. Species at higher trophic levels that rely on the availability of species at lower trophic levels as food may be sensitive to extinction cascades initiated by changes in the habitat of key food resources. Here we assess climate change vulnerability for Ursus arctos (grizzly bears) in the southern Canadian Rocky Mountains using projected changes to 17 of the most commonly consumed plant food items. We used presence-absence information from 7088 field plots to estimate ecological niches and to project changes in future distributions of each species. Model projections indicated idiosyncratic responses among food items. Many food items persisted or even increased, although several species were found to be vulnerable based on declines or geographic shifts in suitable habitat. These included Hedysarum alpinum (alpine sweet vetch), a critical spring and autumn root-digging resource when little else is available. Potential habitat loss was also identified for three fruiting species of lower importance to bears: Empetrum nigrum (crowberry), Vaccinium scoparium (grouseberry), and Fragaria virginiana (strawberry). A general trend towards uphill migration of bear foods may result in higher vulnerability to bear populations at low elevations, which are also those that are most likely to have human-bear conflict problems. Regardless, a wide diet breadth of grizzly bears, as well as wide environmental niches of most food items, make climate change a much lower threat to grizzly bears than other bear species such as polar bears and panda bears. We cannot exclude, however, future alterations in human behavior and land use resulting from climate change that may reduce survival rates.

Douglas-fir plantations in Europe: a retrospective test of assisted migration to address climate change.

We evaluate genetic test plantations of North American Douglas-fir provenances in Europe to quantify how tree populations respond when subjected to climate regime shifts, and we examined whether bioclimate envelope models developed for North America to guide assisted migration under climate change can retrospectively predict the success of these provenance transfers to Europe. The meta-analysis is based on long-term growth data of 2800 provenances transferred to 120 European test sites. The model was generally well suited to predict the best performing provenances along north-south gradients in Western Europe, but failed to predict superior performance of coastal North American populations under continental climate conditions in Eastern Europe. However, model projections appear appropriate when considering additional information regarding adaptation of Douglas-fir provenances to withstand frost and drought, even though the model partially fails in a validation against growth traits alone. We conclude by applying the partially validated model to climate change scenarios for Europe, demonstrating that climate trends observed over the last three decades warrant changes to current use of Douglas-fir provenances in plantation forestry throughout Western and Central Europe.

Genome-wide admixture and ecological niche modelling reveal the maintenance of species boundaries despite long history of interspecific gene flow.

The maintenance of species boundaries despite interspecific gene flow has been a continuous source of interest in evolutionary biology. Many hybridizing species have porous genomes with regions impermeable to introgression, conferring reproductive barriers between species. We used ecological niche modelling to study the glacial and postglacial recolonization patterns between the widely hybridizing spruce species Picea glauca and P. engelmannii in western North America. Genome-wide estimates of admixture based on a panel of 311 candidate gene single nucleotide polymorphisms (SNP) from 290 genes were used to assess levels of admixture and introgression and to identify loci putatively involved in adaptive differences or reproductive barriers between species. Our palaeoclimatic modelling suggests that these two closely related species have a long history of hybridization and introgression, dating to at least 21,000 years ago, yet species integrity is maintained by a combination of strong environmental selection and reduced current interspecific gene flow. Twenty loci showed evidence of divergent selection, including six loci that were both Fst outliers and associated with climatic gradients, and fourteen loci that were either outliers or showed associations with climate. These included genes responsible for carbohydrate metabolism, signal transduction and transcription factors.

Acute lung injury after ruptured abdominal aortic aneurysm repair: the effect of excluding donations from females from the production of fresh frozen plasma.

OBJECTIVES: Transfusion-related acute lung injury may contribute to the development of acute lung injury in the critically ill, due to plasma from female donors containing antileukocyte antibodies. In July 2003, the U.K. National Blood Service stopped using female donor plasma for the production of fresh frozen plasma. Patients undergoing repair of a ruptured abdominal aortic aneurysm receive large amounts of fresh frozen plasma and often develop acute lung injury. We investigated whether the change to male fresh frozen plasma was associated with a change in the frequency of acute lung injury in these patients. DESIGN: A retrospective, before and after, observational, single-center study. SETTING: Tertiary care center and a regional blood center. PATIENTS: The study included 211 patients undergoing open repair of a ruptured abdominal aortic aneurysm between 1998 and 2006. INTERVENTIONS: None. MEASUREMENTS AND MAIN RESULTS: Primary outcome was the development of acute lung injury in the first 6 hrs after surgery. Secondary outcomes were significant hypoxia (PaO2/FiO2 ratio <300), time to extubation, and survival at 30 days. Groups were well matched and received similar volumes of intravenous fluids and blood components. There was significantly less acute lung injury following the change to male fresh frozen plasma (36% before vs. 21% after, p = .04). At 6 hrs after surgery, fewer patients were hypoxic (87% before vs. 62% after, p < .01). In multivariate analysis, the change in donor policy was associated with a decreased risk of developing acute lung injury (odds ratio 0.39; 95% confidence interval, 0.16-0.90). Time to extubation and survival at 30 days were not statistically different between groups. CONCLUSIONS: The policy to exclude female donors from the production of fresh frozen plasma was associated with a decrease in the frequency of acute lung injury in patients undergoing repair of a ruptured abdominal aortic aneurysm.

A biomimetic approach to the detection and identification of estrogen receptor agonists in surface waters using semipermeable membrane devices (SPMDs) and bioassay-directed chemical analysis.

GOAL, SCOPE AND BACKGROUND: Some anthropogenic pollutants posses the capacity to disrupt endogenous control of developmental and reproductive processes in aquatic biota by activating estrogen receptors. Many anthropogenic estrogen receptor agonists (ERAs) are hydrophobic and will therefore readily partition into the abiotic organic carbon phases present in natural waters. This partitioning process effectively reduces the proportion of ERAs readily available for bioconcentration by aquatic biota. Results from some studies have suggested that for many aquatic species, bioconcentration of the freely-dissolved fraction may be the principal route of uptake for hydrophobic pollutants with logarithm n-octanol/water partition coefficient (log Kow) values less than approximately 6.0, which includes the majority of known anthropogenic ERAs. The detection and identification of freely-dissolved readily bioconcentratable ERAs is therefore an important aspect of exposure and risk assessment. However, most studies use conventional techniques to sample total ERA concentrations and in doing so frequently fail to account for bioconcentration of the freely-dissolved fraction. The aim of the current study was to couple the biomimetic sampling properties of semipermeable membrane devices (SPMDs) to a bioassay-directed chemical analysis (BDCA) scheme for the detection and identification of readily bioconcentratable ERAs in surface waters. METHODS: SPMDs were constructed and deployed at a number of sites in Germany and the UK. Following the dialytic recovery of target compounds and size exclusion chromatographic cleanup, SPMD samples were fractionated using a reverse-phase HPLC method calibrated to provide an estimation of target analyte log Kow. A portion of each HPLC fraction was then subjected to the yeast estrogen screen (YES) to determine estrogenic potential. Results were plotted in the form of 'estrograms' which displayed profiles of estrogenic potential as a function of HPLC retention time (i.e. hydrophobicity) for each of the samples. Where significant activity was elicited in the YES, the remaining portion of the respective active fraction was subjected to GC-MS analysis in an attempt to identify the ERAs present. RESULTS AND DISCUSSION: Estrograms from each of the field samples showed that readily bioconcentratable ERAs were present at each of the sampling sites. Estimated log Kow values for the various active fractions ranged from 1.92 to 8.63. For some samples, estrogenic potential was associated with a relatively narrow range of log Kow values whilst in others estrogenic potential was more widely distributed across the respective estrograms. ERAs identified in active fractions included some benzophenones, various nonylphenol isomers, benzyl butyl phthalate, dehydroabietic acid, sitosterol, 3-(4-methylbenzylidine)camphor (4-MBC) and 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN). Other tentatively identified compounds which may have contributed to the observed YES activity included various polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, methylated benzylphenols, various alkyl-phenols and dialkylphenols. However, potential ERAs present in some active fractions remain unidentified. CONCLUSIONS AND OUTLOOK: Our results show that SPMD-YES-based BDCA can be used to detect and identify readily bioconcentratable ERAs in surface waters. As such, this biomimetic approach can be employed as an alternative to conventional methodologies to provide investigators with a more environmentally relevant insight into the distribution and identity of ERAs in surface waters. The use of alternative bioassays also has the potential to expand SPMD-based BDCA to include a wide range of toxicological endpoints. Improvements to the analytical methodology used to identify ERAs or other target compounds in active fractions in the current study could greatly enhance the applicability of the methodology to risk assessment and monitoring programmes.

The photochemistry of N-p-toluenesulfonyl peptides: the peptide bond as an electron donor.

The scope of photobiological processes that involve absorbers within a protein matrix may be limited by the vulnerability of the peptide group to attack by highly reactive redox centers consequent upon electronic excitation. We have explored the nature of this vulnerability by undertaking comprehensive product analyses of aqueous photolysates of 12 N-p-toluenesulfonyl peptides with systematically selected structures. The results indicate that degradation includes a major pathway that is initiated by intramolecular electron transfer in which the peptide bond serves as electron donor, and the data support the likelihood of a relay process in dipeptide derivatives.

Readmission and overstay after day case nasal surgery.

BACKGROUND: A readmission is classified as a patient necessitating readmission to hospital due to a post-operative complication following discharge. An overstay however, is classified as a patient having to stay longer than the planned duration in hospital (not having been discharged in the interim) due to a post-operative complication. This study aims to investigate patient-related factors that predispose to readmission or overstay and thus make recommendations to decrease the likelihood of readmission or overstay. METHOD: In this retrospective study 312 'day-case nasal procedures', were selected from a total cohort of 4274 ENT patients over a 17-month period. This sub-group was investigated for a range of demographic factors including, age, gender and ethnicity with regards to their relationship to readmission rates and overstay frequency and duration. RESULTS: The rates were 2.88% and 9.62% for readmission and overstay respectively. The total number of days spent in hospital as a result of readmission was 27. Epistaxis was the leading cause for readmission/overstay (28.9%) followed by high levels of post-operative pain preventing them from being discharged (23.7%). All procedures in this study had readmission rates that were below those recommended in the guidelines set by the Royal College of Surgeons of England. Women overstayed significantly longer (t = 1.65, p < 0.05) than men. CONCLUSIONS: Suitable candidates for day-case ENT surgery highlighted by this study include healthy individuals between the ages of 20 and 60. Operating in the morning would increase the immediate post-operative recovery time, which may reduce the numbers of patients who complain of high levels of pain at the time of discharge. Procedures such as septorhinoplasty being performed routinely in the ambulatory setting require additional research into more effective methods of pain control. Standards need to be improved so that the causes of overstay and readmission are clearly identifiable in patient records.

Competitive electron transfers from a tyrosyl side-chain and peptide bond in the photodegradation of N-tosyl alpha-aminomethylamides: an insight into photosynthesis and photodamage in the biological oxidation of water?

Photo-excited N-tosyl derivatives of phenylalanyl- and, more particularly, O-methyltyrosylmethylamides undergo electron transfer from aryl to tosyl groups whereas the photo-degradation of aliphatic analogues is initiated by electron transfer from the peptide bond, suggesting the latter as one possible reason for the rapid turnover of the D1 protein in biological water oxidation when the essential mediating role of tyrosine 116 in the PSII complex is inhibited.