Natura 2000 and the regulation of agricultural ammonia emissions

This article provides a comparative analysis of the regulation of ammonia emissions, primarily from livestock installations, in Denmark, Germany and the Netherlands. It discusses the challenges of regulating agricultural ammonia emissions in view of the rulings of the Court of Justice of the European Union (cjeu) on Art. 6(3) of the Habitats Directive. It is argued that the need to ensure certainty concerning the absence of significant effects on Natura 2000 sites is challenged by the uncertainties regarding both the state of individual habitat types and the potential impact of individual projects. A more integrated or programmatic approach may provide an alternative approach to individual assessments, but it is necessary to ensure that additional loads from new or enlarged livestock installations are permitted in areas with high ammonia loads only where it is certain that a programmatic approach will ensure that there are no harmful effects. This might be an almost impossible task

Kelp Forest Ecosystems: Biodiversity, Stability, Resilience and Future

Kelp forests are phyletically diverse, structurally complex and highly productive components of cold-water rocky marine coastlines. This paper reviews the conditions in which kelp forests develop globally and where, why and at what rate they become deforested. The ecology and long archaeological history of kelp forests are examined through case studies from southern California, the Aleutian Islands and the western North Atlantic, well-studied locations that represent the widest possible range in kelp forest biodiversity. Global distribution of kelp forests is physiologically constrained by light at high latitudes and by nutrients, warm temperatures and other macrophytes at low latitudes. Within mid-latitude belts (roughly 40-60degrees latitude in both hemispheres) well-developed kelp forests are most threatened by herbivory, usually from sea urchins. Overfishing and extirpation of highly valued vertebrate apex predators often triggered herbivore population increases, leading to widespread kelp deforestation. Such deforestations have the most profound and lasting impacts on species-depauperate systems, such as those in Alaska and the western North Atlantic. Globally urchin-induced deforestation has been increasing over the past 2-3 decades. Continued fishing down of coastal food webs has resulted in shifting harvesting targets from apex predators to their invertebrate prey, including kelp-grazing herbivores. The recent global expansion of sea urchin harvesting has led to the widespread extirpation of this herbivore, and kelp forests have returned in some locations but, for the first time, these forests are devoid of vertebrate apex predators. In the western North Atlantic, large predatory crabs have recently filled this void and they have become the new apex predator in this system. Similar shifts from fish- to crab-dominance may have occurred in coastal zones of the United Kingdom and Japan, where large predatory finfish were extirpated long ago. Three North American case studies of kelp forests were examined to determine their long history with humans and project the status of future kelp forests to the year 2025. Fishing impacts on kelp forest systems have been both profound and much longer in duration than previously thought. Archaeological data suggest that coastal peoples exploited kelp forest organisms for thousands of years, occasionally resulting in localized losses of apex predators, outbreaks of sea urchin populations and probably small-scale deforestation. Over the past two centuries, commercial exploitation for export led to the extirpation of sea urchin predators, such as the sea otter in the North Pacific and predatory fishes like the cod in the North Atlantic. The largescale removal of predators for export markets increased sea urchin abundances and promoted the decline of kelp forests over vast areas. Despite southern California having one of the longest known associations with coastal kelp forests, widespread deforestation is rare. It is possible that functional redundancies among predators and herbivores make this most diverse system most stable. Such biodiverse kelp forests may also resist invasion from non-native species. In the species-depauperate western North Atlantic, introduced algal competitors carpet the benthos and threaten future kelp dominance. There, other non-native herbivores and predators have become established and dominant components of this system. Climate changes have had measurable impacts on kelp forest ecosystems and efforts to control the emission of greenhouse gasses should be a global priority. However, overfishing appears to be the greatest manageable threat to kelp forest ecosystems over the 2025 time horizon. Management should focus on minimizing fishing impacts and restoring populations of functionally important species in these systems

Catalyst design for Rh-catalysed arene and alkane C-H borylation : the NHC affects the induction period and indenyl is superior to Cp

The authors would like to thank the Royal Society of Chemistry (Undergraduate Summer Research Bursary to A.L.B., Research Fund grant R21-6824221494) and the EPSRC (DTP PhD studentship award to P.A.M., Vacation Internship to L.S., and EP/M024210/1 for supporting B.E.T.) for funding. A.P. thanks the Institute of Chemical Sciences for the award of a bursary to support a summer research project. The authors would also like to thank Johnson Matthey plc for the award of platinum group metal materials used in their research (loan of RhCl3, PGMAS38).In order to establish design criteria for Rh C-H borylation catalysts, analogues of the successful catalyst [Rh(Ind)(SIDipp)(COE)] (Ind = η5-indenyl, SIDipp = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene, COE = cis-cyclooctene) were synthesised by changing the indenyl and carbene ligands. [RhCp(SIDipp)(COE)] (1) formed alongside the C-C activated, cyclometallated by-product [RhCp(κ2CAr,Ccarbene-SIDippʹ)(iPr)] (rac-2; SIDippʹ = 1-(6-isopropylphenyl)-3-(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene). Computational modelling of COE dissociation showed that both C-C and C-H activation of the SIDipp aryl group is thermally attainable and reversible under experimental conditions, with the C-C activation products the more thermodynamically stable species. Oxidative addition of 1 with SiH(OEt)3 gave the Rh silyl hydride [RhCp(H){Si(OEt)3}(SIDipp)] (rac-3). [Rh(Ind)(IDipp)(COE)] (4; IDipp = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene), the carbonyl analogue [Rh(Ind)(IDipp)(CO)] (5; νCO = 1940 cm-1, c.f. 1944 cm-1 for [Rh(Ind)(SIDipp)(COE)]) and [Rh(Ind)(IMe4)(COE)] (6; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) were also characterised, but attempts to synthesise Rh carbene complexes with fluorenyl or 1,2,3,4-tetrahydrofluorenyl ligands were not successful. For the catalytic C-H borylation of benzene using B2pin2, 1 was inactive at 80°C, and [Rh(Ind)(SIDipp)(COE)] was superior to all other complexes tested due to the shortest induction period. However, addition of HBpin to precatalyst 4 eliminated the induction period. Catalytic n-alkane C-H borylation using [Rh(Ind)(NHC)(COE)] gave yields of up to 21% alkylBpin but [RhCp*(C2H4)2] was the better catalyst.Peer reviewe

Neurochemical Aftermath of Repetitive Mild Traumatic Brain Injury

IMPORTANCE: Evidence is accumulating that repeated mild traumatic brain injury (mTBI) incidents can lead to persistent, long-term debilitating symptoms and in some cases a progressive neurodegenerative condition referred to as chronic traumatic encephalopathy. However, to our knowledge, there are no objective tools to examine to which degree persistent symptoms after mTBI are caused by neuronal injury. OBJECTIVE: To determine whether persistent symptoms after mTBI are associated with brain injury as evaluated by cerebrospinal fluid biochemical markers for axonal damage and other aspects of central nervous system injury. DESIGN, SETTINGS, AND PARTICIPANTS: A multicenter cross-sectional study involving professional Swedish ice hockey players who have had repeated mTBI, had postconcussion symptoms for more than 3 months, and fulfilled the criteria for postconcussion syndrome (PCS) according to the Diagnostic and Statistical Manual of Mental Disorders (Fourth Edition) matched with neurologically healthy control individuals. The participants were enrolled between January 2014 and February 2016. The players were also assessed with Rivermead Post Concussion Symptoms Questionnaire and magnetic resonance imaging. MAIN OUTCOMES AND MEASURES: Neurofilament light protein, total tau, glial fibrillary acidic protein, amyloid β, phosphorylated tau, and neurogranin concentrations in cerebrospinal fluid. RESULTS: A total of 31 participants (16 men with PCS; median age, 31 years; range, 22-53 years; and 15 control individuals [11 men and 4 women]; median age, 25 years; range, 21-35 years) were assessed. Of 16 players with PCS, 9 had PCS symptoms for more than 1 year, while the remaining 7 returned to play within a year. Neurofilament light proteins were significantly increased in players with PCS for more than 1 year (median, 410 pg/mL; range, 230-1440 pg/mL) compared with players whose PCS resolved within 1 year (median, 210 pg/mL; range, 140-460 pg/mL) as well as control individuals (median 238 pg/mL, range 128-526 pg/mL; P = .04 and P = .02, respectively). Furthermore, neurofilament light protein concentrations correlated with Rivermead Post Concussion Symptoms Questionnaire scores and lifetime concussion events (ρ = 0.58, P = .02 and ρ = 0.52, P = .04, respectively). Overall, players with PCS had significantly lower cerebrospinal fluid amyloid-β levels compared with control individuals (median, 1094 pg/mL; range, 845-1305 pg/mL; P = .05). CONCLUSIONS AND RELEVANCE: Increased cerebrospinal fluid neurofilament light proteins and reduced amyloid β were observed in patients with PCS, suggestive of axonal white matter injury and amyloid deposition. Measurement of these biomarkers may be an objective tool to assess the degree of central nervous system injury in individuals with PCS and to distinguish individuals who are at risk of developing chronic traumatic encephalopathy

Effects of training on postural control and agility when wearing socks of different compression levels

Study aim: The aim of this study was to evaluate the effects of training while wearing socks differing in compression level (clinical, sub-clinical, regular) on performance of static and dynamic balancing and agility tasks in healthy, physically active people. We sought to understand whether socks with different compression properties supported postural regulation and agility task performance by enhancing somatosensory perception, unskewed by specific age range effects. Material and methods: Participants comprised 61 adults aged 18-75 years, divided into three groups (two experimental groups wearing clinical or sub-clinical level compression socks, and one control group wearing regular non-compression socks during training). An 8-week (2 × 1h per week) intervention programme was administered to train static and dynamic balance and postural control, leg strength and agility. Results: A mixed model ANOVA revealed no differences in static and dynamic balance and postural control and agility performance between clinical, sub-clinical, and control groups before and after training. All groups significantly improved their test performance, suggesting that training had some benefit on motor performance. Conclusions: These results raised interesting questions requiring further investigation to examine the effects of wearing socks (with and without different levels of compression) on motor behaviours in specific groups of elderly vs. young participants, in physically active vs. less physically active people, and in performance settings outside standardized laboratory tests to study applications in natural performance environments

A Structurally Characterized Cobalt(I) σ-Alkane Complex

The synthesis, and x-ray structure, of a cobalt s -alkane complex, [Co(Cy 2 P(CH 2 ) 4 PCy 2 )( norbornane )][BAr F 4 ], is achieved by a single-crystal to single-crystal solid/gas hydrogenation from a norbornadiene precursor. Magnetic data show this complex to be a triplet. Periodic DFT and electronic structure analyses identify weak C-H ··· Co σ -interactions, augmented by dispersive stabilisation between the alkane ligand and the anion-microenvironment. The calculations are most consistent with a η 1 : η 1 -alkane binding mode