Methods for synthesis of nonabromodiphenyl ethers and a chloro-nonabromodiphenyl ether

Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants (BFRs) in textiles, upholstery and electronics. They are ubiquitous contaminants in wildlife and humans. A low concentration of nonabrominated diphenyl ethers (nonaBDEs) is present in commercial DecaBDE and they are also abiotic and biotic debromination products of decabromodiphenyl ether (BDE-209). The objective of the present work was to develop methods for synthesis of the three nonaBDEs, 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether (BDE-206), 2,2',3,3',4,4',5,6,6'-nonabromodiphenyl ether (BDE-207) and 2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (BDE-208), with the intention of making them available as authentic standards for analytical, toxicological and stability studies, as well as studies regarding physical-chemical properties. Two methods were developed, one based on perbromination of phenoxyanilines and the other via reductive debromination of BDE-209 by sodium borohydride followed by chromatographic separation of the three nonaBDE isomers formed. An additional nonabrominated compound, 4'-chloro-2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (Cl-BDE-208), was also synthesized in the present work. Cl-BDE-208, prepared by the perbromination of 4-chlorodiphenyl ether, may be used as an internal standard in analysis of highly brominated diphenyl ethers. BDE-206, BDE-207, BDE-208 and Cl-BDE-208 were characterized by 1H NMR, 13C NMR, electron ionization mass spectra and by their melting points. The structures of all three nonaBDEs have been characterized previously by X-ray crystallography.     

Using vertebrate environmental DNA from seawater in biomonitoring of marine habitats

Conservation and management of marine biodiversity depends on biomonitoring of marine habitats, but current approaches are resource-intensive and require different approaches for different organisms. Environmental DNA (eDNA) extracted from water samples is an efficient and versatile approach to detecting aquatic animals. In the ocean, eDNA composition reflects local fauna at fine spatial scales, but little is known about the effectiveness of eDNA-based monitoring of marine communities at larger scales. We investigated the potential of eDNA to characterize and distinguish marine communities at large spatial scales by comparing vertebrate species composition among marine habitats in Qatar, the Arabian Gulf (also known as the Persian Gulf), based on eDNA metabarcoding of seawater samples. We conducted species accumulation analyses to estimate how much of the vertebrate diversity we detected. We obtained eDNA sequences from a diverse assemblage of marine vertebrates, spanning 191 taxa in 73 families. These included rare and endangered species and covered 36% of the bony fish genera previously recorded in the Gulf. Sites of similar habitat type were also similar in eDNA composition. The species accumulation analyses showed that the number of sample replicates was insufficient for some sampling sites but suggested that a few hundred eDNA samples could potentially capture >90% of the marine vertebrate diversity in the study area. Our results confirm that seawater samples contain habitat-characteristic molecular signatures and that eDNA monitoring can efficiently cover vertebrate diversity at scales relevant to national and regional conservation and management.     

Deriving heart rate variability indices from cardiac monitoring—An indicator of driver sleepiness

Objective: Driver fatigue is considered to be a major contributor to road traffic crashes. Cardiac monitoring and heart rate variability (HRV) analysis is a candidate method for early and accurate detection of driver sleepiness. This study has 2 objectives: to evaluate the (1) suitability of different preprocessing strategies for detecting and removing outlier heartbeats and spectral transformation of HRV signals and their impact of driver sleepiness assessment and (2) relation between common HRV indices and subjective sleepiness reported by a large number of drivers in real driving situations, for the first time.

Methods: The study analyzed >3,500 5-min driving epochs from 76 drivers on a public motorway in Sweden. The electrocardiograph (ECG) data were recorded in 3 studies designed to evaluate the physiological differences between awake and sleepy drivers. The drivers reported their perceived level of sleepiness according to the Karolinska Sleepiness Scale (KSS) every 5?min. Two standard methods were used for identifying outlier heartbeats: (1) percentage change (PC), where outliers were defined as interbeat intervals deviating >30% from the mean of the four previous intervals and (2) standard deviation (SD), where outliers were defined as interbeat interval deviating >4 SD from the mean interval duration in the current epoch. Three standard methods were used for spectral transformation, which is needed for deriving HRV indices in the frequency domain: (1) Fourier transform; (2) autoregressive model; and (3) Lomb-Scargle periodogram. Different preprocessing strategies were compared regarding their impact on derivation of common HRV indices and their relation to KSS data distribution, using box plots and statistical tests such as analysis of variance (ANOVA) and Student’s t test.

Results: The ability of HRV indices to discriminate between alert and sleepy drivers does not differ significantly depending on which outlier detection and spectral transformation methods are used. As expected, with increasing sleepiness, the heart rate decreased, whereas heart rate variability overall increased. Furthermore, HRV parameters representing the parasympathetic branch of the autonomous nervous system increased. An unexpected finding was that parameters representing the sympathetic branch of the autonomous nervous system also increased with increasing KSS level. We hypothesize that this increment was due to stress induced by trying to avoid an incident, because the drivers were in real driving situations.

Conclusions: The association of HRV indices to KSS did not depend on the preprocessing strategy. No preprocessing method showed superiority for HRV association to driver sleepiness. This was also true for combinations of methods for frequency domain HRV indices. The results prove clear relationships between HRV indices and perceived sleepiness. Thus, HRV analysis shows promise for driver sleepiness detection.     

What limits predator detection in blue tits (<Emphasis Type="Italic">Parus caeruleus</Emphasis>): posture,task or orientation?

To detect threats and reduce predation risk prey animals need to be alert. Early predator detection and rapid anti-predatory action increase the likelihood of survival. We investigated how foraging affects predator detection and time to take-off in blue tits (Parus caeruleus) by subjecting them to a simulated raptor attack. To investigate the impact of body posture we compared birds feeding head-down with birds feeding head-up, but could not find any effect of posture on either time to detection or time to take-off. To investigate the impact of orientation we compared birds having their side towards the attacking predator with birds having their back towards it. Predator detection, but not time to take-off, was delayed when the back was oriented towards the predator. We also investigated the impact of foraging task by comparing birds that were either not foraging, foraging on chopped mealworms, or foraging on whole ones. Foraging on chopped mealworms did not delay detection compared to nonforaging showing that foraging does not always restrict vigilance. However, detection was delayed more than 150% when the birds were foraging on whole, live mealworms, which apparently demanded much attention and handling skill. Time to take-off was affected by foraging task in the same way as detection was. We show that when studying foraging and vigilance one must include the difficulty of the foraging task and prey orientation.Communicated by P.A. Bednekoff     

Aluminium metabolism in chronic renat failure: Environmental influences and regional differences in Norway

Many aspects of Al metabolism in chronic renal failure are poorly understood. A longitudinal study of serum Al concentrations in predialysis patients and healthy control subjects revealed very high values during the autumn of 1984 and 1985. Renal Al clearance was low during the autumnal spike in serum Al but increased substantially when the serum Al concentration declined. A second study confirmed that by using citric acid as a chelator, the gastrointestinal absorption of Al from Al(OH)₃ may be considerably augmented as reflected by increases in both serum Al concentrations and renal Al clearance. The individual differences in Al absorption in this study were large.The first study suggests the existence of an unidentified environmental factor, possibly water borne, with profound effects on Al absorption and excretion. The citric acid/Al(OH)₃ experiment suggests that the existence of such a factor is likely. The implications of these results are not known.A histomorphometric study of bone biopsies from 138 hemodialysis and 66 predialysis patients without clinical evidence of Al related disease, revealed Al deposits after staining with aurin tricarboxylic acid in 78% of the biopsies from the former and 24% of the latter patients. Serum Al concentrations did not differ between predialysis and hemodialysis patients with Al positive biopsies. Stratification of the hemodialysis patients, who came from all parts of Norway, revealed that patients living in regions with slightly Al contaminated drinking water (Al <30 g/L) had lower serum Al concentrations than patients from regions with highly contaminated water (Al >100 g/L). The prevalence of Al-positive biopsies was the same in both regions. Patients with Al-positive biopsies did not differ in serum Al level from those with Al-negative biopsies within the same region. Predialysis patients with Al-positive biopsies had significantly higher serum Al levels than predialysis patients with Al negative biopsies.Stainable Al deposits are commonly found in the bone of patients with chronic renal failure. Cross-sectionally obtained serum Al concentrations do not reflect the prevalence of stainable bone Al in renal patients but are related to the degree of Al contamination of water of the region.     

Split-second escape decisions in blue tits (Parus caeruleus)

Bird mortality is heavily affected by birds of prey. Under attack, take-off is crucial for survival and even minor mistakes in initial escape response can have devastating consequences. Birds may respond differently depending on the character of the predator's attack and these split-second decisions were studied using a model merlin (Falco columbarius) that attacked feeding blue tits (Parus caeruleus) from two different attack angles in two different speeds. When attacked from a low attack angle they took off more steeply than when attacked from a high angle. This is the first study to show that escape behaviour also depends on predator attack speed. The blue tits responded to a high-speed attack by dodging sideways more often than when attacked at a low speed. Escape speed was not significantly affected by the different treatments. Although they have only a split-second before escaping an attack, blue tits do adjust their escape strategy to the prevailing attack conditions.     

A multidisciplinary study of archaeological grape seeds

We report here the first integrated investigation of both ancient DNA and proteins in archaeobotanical samples: medieval grape (Vitis vinifera L.) seeds, preserved by anoxic waterlogging, from an early medieval (seventh–eighth century A.D.) Byzantine rural settlement in the Salento area (Lecce, Italy) and a late (fourteenth–fifteenth century A.D.) medieval site in York (England). Pyrolysis gas chromatography mass spectrometry documented good carbohydrate preservation, whilst amino acid analysis revealed approximately 90% loss of the original protein content. In the York sample, mass spectrometry-based sequencing identified several degraded ancient peptides. Nuclear microsatellite locus (VVS2, VVMD5, VVMD7, ZAG62 and ZAG79) analysis permitted a tentative comparison of the genetic profiles of both the ancient samples with the modern varieties. The ability to recover microsatellite DNA has potential to improve biomolecular analysis on ancient grape seeds from archaeological contexts. Although the investigation of five microsatellite loci cannot assign the ancient samples to any geographic region or modern cultivar, the results allow speculation that the material from York was not grown locally, whilst the remains from Supersano could represent a trace of contacts with the eastern Mediterranean.     

Interdisciplinary knowledge integration through group model building: recognizing dualities and triadizing the conversation

As part of the inquiry into managing an interdisciplinary research process on adaptive water governance, we investigated the process of group model building (GMB) and, more specifically, the role of Unified Modeling Language (UML) in this process. An analysis of group interaction reveals several tensions in the process of knowledge integration, which can be grouped into three overarching dualities: ‘simplicity versus complexity’, ‘constraining versus containing’ and ‘defining versus refining’. As group members take different positions with regard to these dualities, these represent sources of tension and potential ‘stuckness’ of the GMB. Hence the question arises how the group can manage duality in ways that take the GMB beyond its opposing forces. We suggest that knowledge integration processes may benefit from early recognition of the dualities at hand and strategies aimed at creating ‘thirdness’, including some suggestions on the concrete forms such ‘thirdness’ may take.     

Is habitat amount important for biodiversity in rocky shore systems? A study of South African mussel assemblages

Habitat-forming species on rocky shores are often subject to high levels of exploitation, but the effects of subsequent habitat loss and fragmentation on associated species and the ecosystem as a whole are poorly understood. In this study, the effects of habitat amount on the fauna associated with mussel beds were investigated, testing for the existence of threshold effects at small landscape scales. Specifically, the relationships between mussel or algal habitat amount and: associated biodiversity, associated macrofaunal abundance and density of mussel recruits were studied at three sites (Kidd’s Beach, Kayser’s Beach and Kini Bay) on the southern and south-eastern coasts of South Africa. Samples, including mussel-associated macrofauna, of 10 × 10 cm were taken from areas with 100 % mussel cover (Perna perna or a combination of P. perna and Mytilus galloprovincialis) at each site. The amount of habitat provided by mussels and algae surrounding the sampled areas was thereafter determined at the 4.0 m² scale. A number of significant positive relationships were found between the amount of surrounding mussel habitat and the abundances of several taxa (Anthozoa, Malacostraca and Nemertea). Likewise, there were positive relationships between the amount of surrounding algal habitat and total animal abundance as well as abundance of mussel recruits at one site, Kini Bay. In contrast, abundance of mussel recruits showed a significant negative relationship with the amount of mussel habitat at Kayser’s Beach. Significant negative relationships were also detected between the amount of mussel habitat and species richness and total abundance at Kidd’s Beach, and between amount of mussel habitat and the abundance of many taxa (Bivalvia, Gastropoda, Maxillopoda, Ophiuroidea, Polychaeta and Pycnogonida) at all three sites. No threshold effects were found, nor were significant relationships consistent across the investigated sites. The results indicate that the surrounding landscape is important in shaping the structure of communities associated with these mussel beds, with significant effects of the amount of surrounding habitat per se. The strength and the direction of habitat effects vary, however, between shores and probably with the scale of observation as well as with the studied dependent variables (e.g. diversity, abundance, mussel recruitment, species identity), indicating the complexity of the processes structuring macrofaunal communities on these shores.     

Seasonal modulation of flight speed among nocturnal passerine migrants: differences between short- and long-distance migrants

Migrating birds are expected to fly at higher airspeeds when minimizing time rather than energy costs of their migratory journeys. Spring migration has often been suggested to be more time selected than autumn migration, because of the advantage of early arrival at breeding sites. We have earlier demonstrated that nocturnal passerine migrants fly at higher airspeeds during spring compared to autumn, supporting time-selected spring migration. In this study, we test the hypothesis that seasonal airspeeds are modulated differently between short- and long-distance migrants, because of a stronger element of time selection for autumn migration over long distances. In support of this hypothesis, we demonstrate that the seasonal difference in airspeed is significantly larger (spring airspeed exceeding autumn airspeed by a factor of 1.16 after correcting for the influence of altitude, wind and climb/descent on airspeed) among short-distance compared to long-distance (factor 1.12) migrants. This result is based on a large sample of tracking radar data from 3 years at Falsterbo, South Sweden. Short-distance migrants also tend to fly with more favourable winds during autumn, indicating relaxed time constraints (being able to afford to wait for favourable winds) compared to long-distance migrants. These results indicate surprisingly fine-tuned seasonal modulation of airspeed and responses to wind, associated with behavioural strategies adapted to different levels of time selection pressures during spring and autumn migration.