Harbour porpoises (Phocoena phocoena) and wind farms: a case study in the Dutch North Sea

The rapid increase in development of offshore wind energy in European waters has raised concern for the possible environmental impacts of wind farms. We studied whether harbour porpoise occurrence has been affected by the presence of the Dutch offshore wind farm Egmond aan Zee. This was done by studying acoustic activity of porpoises in the wind farm and in two reference areas using stationary acoustic monitoring (with T-PODs) prior to construction (baseline: June 2003 to June 2004) and during normal operation of the wind farm (operation: April 2007 to April 2009). The results show a strong seasonal pattern, with more activity recorded during winter months. There was also an overall increase in acoustic activity from baseline to operation, in line with a general increase in porpoise abundance in Dutch waters over the last decade. The acoustic activity was significantly higher inside the wind farm than in the reference areas, indicating that the occurrence of porpoises in this area increased as well. The reasons of this apparent preference for the wind farm area are not clear. Two possible causes are discussed: an increased food availability inside the wind farm (reef effect) and/or the absence of vessels in an otherwise heavily trafficked part of the North Sea (sheltering effect

Three-Dimensional X-Ray Photoelectron Tomography on the Nanoscale: Limits of Data Processing by Principal Component Analysis

AbstractIn a previous article, we studied the influence of spectral noise on a new method for three-dimensional X-ray photoelectron spectroscopy (3D XPS) imaging, which is based on analysis of the XPS peak shape [Hajati, S., Tougaard, S., Walton, J. &amp; Fairley, N. (2008). Surf Sci602, 3064–3070]. Here, we study in more detail the influence of noise reduction by principal component analysis (PCA) on 3D XPS images of carbon contamination of a patterned oxidized silicon sample and on 3D XPS images of Ag covered by a nanoscale patterned octadiene layer. PCA is very efficient for noise reduction, and using only the three most significant PCA factors to reconstruct the spectra restores essentially all physical information in both the intensity and shape of the XPS spectra. The corresponding signal-to-noise improvement was estimated to be equivalent to a reduction by a factor of 200 in the required data acquisition time. A small additional amount of information is obtained by using up to five PCA factors, but due to the increased noise level, this information can only be extracted if the intensity of the start and end points for each spectrum are obtained as averages over several energy points.</jats:p

Quantitative analysis of Ni 2p photoemission in NiO and Ni diluted in a SiO2 matrix

In X-ray excited photoelectron emission (XPS), besides the initial excitation process, the shape and intensity of photoelectron peaks are strongly affected by extrinsic excitations due to electron transport out of the surface (including bulk and surface effects) and to intrinsic excitations due to the sudden creation of the static core hole. To make an accurate quantitative interpretation of features observed in XPS, these effects must be included in the theoretical description of the emitted photoelectron spectra. It was previously shown [N. Pauly, S. Tougaard, F. Yubero, Surf. Sci. 620 (2014) 17] that these three effects can be calculated by means of the QUEELS-XPS software (QUantitative analysis of Electron Energy Losses at Surfaces for XPS) in terms of effective energy-differential inelastic electron scattering cross-sections. The only input needed to calculate these cross-sections is the energy loss function of the media which is determined from analysis of Reflection Electron Energy Loss Spectra (REELS). The full XPS spectrum is then modeled by convoluting this energy loss cross-section with the primary excitation spectrum that accounts for all effects which are part of the initial photo-excitation process, i.e. lifetime broadening, spin-orbit coupling, and multiplet splitting. In this paper we apply the previously presented procedure to the study of Ni 2p photoemission in NiO and Ni diluted in a SiO 2 matrix (Ni:SiO 2), samples being prepared by reactive magnetron sputtering at room temperature. We observe a significant difference between the corresponding Ni 2p primary excitation spectra. The procedure allows quantifying the relative intensity of the c3d 9L, c3d 10L 2, and c3d 8 final states contributing to the Ni 2p photoemission spectra of the Ni 2 + species in the oxide matrices. Especially, the intensity ratio in NiO between the non-local and local contributions to the 3d 9L configuration is determined to be 2.5. Moreover the relative intensity ratio of the c3d 9L/c3d 10L 2/c3d 8 configurations is found to be 1.0/0.83/0.11 for both the NiO and Ni:SiO 2 samples.</p

On the ultrathin gold film used as buffer layer at the transparent conductive anode/organic electron donor interface

Previously, we have shown that a gold thin film of only 0.5 nm introduced at the interface between the indium tin oxide or ZnO anode and the organic electron donor in organic photovoltaic cells induces a strong improvement of the cell efficiency. Of course a thickness of 0.5 nm corresponds only to an averaged thickness, the films being too thin to be continuous. For a clear understanding of the physical mechanisms that are responsible for this improved behaviour, it is important to know the fractional coverage and the island height of this thin Au film. In the present work, we have used two different techniques, such as treated scanning electron microscope images and analysis of the inelastic part of peaks of X-ray photoelectron spectroscopy spectra, to estimate the gold coverage and island height of the transparent conductive anode. There is an excellent agreement between the results achieved by both methods. Only 15% of the anode is covered, which proves the high efficiency of gold as an anode buffer layer in organic photovoltaic devices

Bulk and surface switching in Mn-Fe-based Prussian Blue Analogues

Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.Comment: 12 pages, 8 figure

Stomach contents of sperm whales Physeter macrocephalus stranded in the North Sea 1990-1996

Stomach contents of 17 sperm whales Physeter macrocephalus stranded in Scotland and Denmark during 1990-96 were analysed. All were sub-adult or adult males and stranded between November and March. They had presumably entered the North Sea during their southward migration from feeding grounds in Arctic waters. Other studies indicate that the majority of the whales were apparently healthy. The diet of these whales was found to consist almost entirely of cephalopods, principally squid of the genus Gonatus (hereafter 'Gonatus', but probably G. fabricii, an oceanic species characteristic of Arctic waters). The other prey species identified were also mostly oceanic cephalopods: the squids Histioteuthis bonnellii, Teuthowenia megalops and Todarodes sagittatus and the octopus Haliphron atlanticus. Although these results are consistent with other recent studies in the area based on single stranded whales, they differ from results of work on whales caught during commercial whaling operations in Icelandic waters (1960s to 1980s) in that little evidence of predation on fish was found in the present study. Remains of single individuals of the veined squid Loligo forbesi, the northern octopus Eledone cirrhosa and the saithe Pollachius virens provided the only possible evidence of feeding in the North Sea. We infer that sperm whales do not enter the North Sea to feed. The timing, and large and uniform sizes of the Gonatus species eaten (most had mantle lengths in the range 195 to 245 mm), as estimated from measurements of the lower beaks, and the seasonality of the strandings is consistent with the whales having fed on mature squid, possibly spawning concentrations--as has recently been reported for bottlenose whales. Assuming that the diet recorded in this study was representative of sperm whales during the feeding season, as much as 500000 t of Gonatus could be removed by sperm whales in Norwegian waters each year and up to 3 times that figure from the eastern North Atlantic as a whole. Evidence from other studies indicates that Gonatus is an important food resource for a wide range of marine predators in Arctic waters

Cetacean noise criteria revisited in the light of proposed exposure limits for harbour porpoises

The impact of underwater noise on marine life calls for identification of exposure criteria to inform mitigation. Here we review recent experimental evidence with focus on the high-frequency cetaceans and discuss scientifically-based initial exposure criteria. A range of new TTS experiments suggest that harbour and finless porpoises are more sensitive to sound than expected from extrapolations based on results from bottlenose dolphins. Furthermore, the results from TTS experiments and field studies of behavioural reactions to noise, suggest that response thresholds and TTS critically depend on stimulus frequency. Sound exposure levels for pure tones that induce TTS are reasonably consistent at about 100 dB above the hearing threshold for pure tones and sound pressure thresholds for avoidance reactions are in the range of 40-50 dB above the hearing threshold. We propose that frequency weighting with a filter function approximating the inversed audiogram might be appropriate when assessing impact

XPS quantification with universal inelastic electron scattering cross section including intrinsic excitations

In X-ray excited photoelectron emission (XPS), the shape and intensity of photoelectron peaks are strongly affected by extrinsic excitations due to electron transport out of the surface. It is also influenced by intrinsic excitations due to the sudden creation of the static core hole. In order to approximately determine the primary excitation spectrum of the considered transition corrected for both extrinsic and intrinsic excitations, we developed in a previous work [E. Gnacadja, N. Pauly, S. Tougaard, Surf. Interface Anal. 52 (2020) 413] a universal analytical expression for the energy loss cross section including extrinsic and intrinsic excitations. We apply the present universal cross section to test to what extent these primary excitations spectra can be used for XPS quantification based on peak area ratios. The procedure is applied to the study of three sets of polycrystalline alloys (Cu0.75Au0.25, Cu0.50Au0.50, and Cu0.25Au0.75) and to three metal oxides (HfO2, ZrO2, and Cu2O). We show that although the individual peaks are very different from those obtained with the classical universal Tougaard cross section, the determined quantitative compositions are equivalent (but not better). This implies that the relative contribution from intrinsic excitations is roughly the same for all peaks for a given sample and they therefore cancel out when peak area ratios are considered.</p

Characteristics and propagation of airgun pulses in shallow water with implications for effects on small marine mammals

Airguns used in seismic surveys are among the most prevalent and powerful anthropogenic noise sources in marine habitats. They are designed to produce most energy below 100 Hz, but the pulses have also been reported to contain medium-to-high frequency components with the potential to affect small marine mammals, which have their best hearing sensitivity at higher frequencies. In shallow water environments, inhabited by many of such species, the impact of airgun noise may be particularly challenging to assess due to complex propagation conditions. To alleviate the current lack of knowledge on the characteristics and propagation of airgun pulses in shallow water with implications for effects on small marine mammals, we recorded pulses from a single airgun with three operating volumes (10 in3, 25 in3 and 40 in3) at six ranges (6, 120, 200, 400, 800 and 1300 m) in a uniform shallow water habitat using two calibrated Reson 4014 hydrophones and four DSG-Ocean acoustic data recorders. We show that airgun pulses in this shallow habitat propagated out to 1300 meters in a way that can be approximated by a 18log(r) geometric transmission loss model, but with a high pass filter effect from the shallow water depth. Source levels were back-calculated to 192 dB re µPa2s (sound exposure level) and 200 dB re 1 µPa dB Leq-fast (rms over 125 ms duration), and the pulses contained substantial energy up to 10 kHz, even at the furthest recording station at 1300 meters. We conclude that the risk of causing hearing damage when using single airguns in shallow waters is small for both pinnipeds and porpoises. However, there is substantial potential for significant behavioral responses out to several km from the airgun, well beyond the commonly used shut-down zone of 500 meters