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Oxygen isotope (δ18O) sclerochronology of benthic marine molluscs provides a means of reconstructing the seasonal range in seafloor temperature, subject to use of an appropriate equation relating shell δ18O to temperature and water δ18O, a reasonably accurate estimation of water δ18O, and due consideration of growth-rate effects. Taking these factors into account, δ18O data from late Pliocene bivalves of the southern North Sea basin (Belgium and the Netherlands) indicate a seasonal seafloor range a little smaller than now in the area. Microgrowth-increment data from Aequipecten opercularis, together with the species composition of the bivalve assemblage and aspects of preservation, suggest a setting below the summer thermocline for all but the latest material investigated. This implies a higher summer temperature at the surface than on the seafloor and consequently a greater seasonal range. A reasonable (3 ∘C) estimate of the difference between maximum seafloor and surface temperature under circumstances of summer stratification points to seasonal surface ranges in excess of the present value (12.4 ∘C nearby). Using a model-derived estimate of water δ18O (0.0 ‰), summer surface temperature was initially in the cool temperate range ( ∘C) and then (during the Mid-Piacenzian Warm Period; MPWP) increased into the warm temperate range (>20 ∘C) before reverting to cool temperate values (in conjunction with shallowing and a loss of summer stratification). This pattern is in agreement with biotic-assemblage evidence. Winter temperature was firmly in the cool temperate range ( ∘C) throughout, contrary to previous interpretations. Averaging of summer and winter surface temperatures for the MPWP provides a figure for annual sea surface temperature that is 2–3 ∘C higher than the present value (10.9 ∘C nearby) and in close agreement with a figure obtained by averaging alkenone and TEX86 temperatures for the MPWP from the Netherlands. These proxies, however, respectively, underestimate summer temperature and overestimate winter temperature, giving an incomplete picture of seasonality. A higher annual temperature than now is consistent with the notion of global warmth in the MPWP, but a low winter temperature in the southern North Sea basin suggests regional reduction in oceanic heat supply, contrasting with other interpretations of North Atlantic oceanography during the interval. Carbonate clumped isotope (Δ47) and biomineral unit thermometry offer means of checking the δ18O-based temperatures.

Analogous to the ubiquitous alkoxide ligand, metal boroxide and boryloxy complexes are an underexplored class of hard anionic O– ligand. A new series of amine-stabilized Li, Sn(II), and Zn boryloxy complexes, comprising electron-rich tetrahedral boron centers have been synthesized and characterized. All complexes have been characterized by one-dimensional (1D), two-dimensional (2D), and DOSY NMR, which are consistent with the solid-state structures unambiguously determined via single-crystal X-ray diffraction. Electron-rich μ2- (Sn and Zn) and μ3- (Li) boryloxy binding modes are observed. Compounds 6–9 are the first complexes of this class, with the chelating bis- and tris-phenol ligands providing a scaffold that can be easily functionalized and provides access to the boronic acid pro-ligand, hence allowing facile direct synthesis of the resulting compounds. Computational quantum chemical studies suggest a significant enhancement of the π-donor ability of the amine-stabilized boryloxy ligand because of electron donation from the amine functionality into the p-orbital of the boron atom.

Here we report the development of a new scalable and transferable plasma assisted atomic layer deposition (PEALD) process for the production of uniform, conformal and pinhole free NiO with sub-nanometre control on a commercial ALD reactor. In this work we use the readily available nickel precursor nickelocene in conjunction with O2 plasma as a co-reagent (100 W) over a temperature range of 75–325 °C. An optimised growth per cycle of 0.036 nm was obtained at 250 °C with uniform thickness and coverage on scale-up to and including an 6 inch Si wafer (with a 200 nm thermal SiO2 top layer). The bulk characteristics of the NiO thin films were comprehensively interrogated by PXRD, Raman spectroscopy, UV-vis spectroscopy and XPS. The new NiO process was subsequently used to fabricate a 3D nanostructured NiO/TiO2/FTO heterojunction by depositing 20 nm of NiO onto pre-fashioned TiO2 nanorods at 250 °C for application in the photo-electrolysis of water in a photoelectrochemical cell (PEC). The NiO/TiO2 3D array was shown to possess a peak current of 0.38 mA cm−2 at 1.23 VRHE when stimulated with a one sun lamp.

Water splitting in photoelectrochemical cells is a promising technology to produce solar hydrogen. Fe2TiO5 pseudobrookite with a bandgap of around 2 eV absorbs the predominant visible range of the ...

Photo-generated high-energy surface states can help to produce chlorine in aqueous environments. Here, aligned rutile (TiO2) nanocrystal arrays are grown onto fluorine-doped tin oxide (FTO) substrates and activated either by hydrothermal Sr/Ba surface doping and/or by vacuum-annealing. With vacuum-annealing, highly photoactive films are obtained with photocurrents of typically 8 mA cm−2 at 1.0 V vs. SCE in 1 M KCl (LED illumination with λ = 385 nm and approx. 100 mW cm−2). Photoelectrochemical chlorine production is demonstrated at proof-of-concept scale in 4 M NaCl and suggested to be linked mainly to the production of Ti(III) surface species by vacuum-annealing, as detected by post-catalysis XPS, rather than to Sr/Ba doping at the rutile surface. The vacuum-annealing treatment is proposed to beneficially affect (i) bulk semiconductor TiO2 nanocrystal properties and electron harvesting, (ii) surface TiO2 reactivity towards chloride adsorption and oxidation, and (iii) FTO substrate performance.

Water splitting by photocatalysis, for example employing seawater or wastewater, has the potential to make a substantial contribution to a future hydrogen economy. New types of 3D metal-wire substrates in woven form or brushes for photoelectrochemical processes are desirable to replace flat semiconductor-coated surfaces. In this report, titanium microwires (100 m diameter; pre-passivated) are employed to produce high surface area photoanodes with a TiO2 (rutile) nanocrystal array coating that was grown hydrothermally. A photo-active electrode is obtained with nanocrystal TiO2 rods of adjustable length from 1.67 µm up to 7.38 µm. Saturation of the photoelectrochemical response occurs at an intermediate length of approx. 3.19 µm with a photocurrent density of approximately 4.4 mA cm-2 at 1.0 V vs. Ag/AgCl (3M) in aqueous 1 M Na2SO4 under 100 mW cm-2 385 nm LED illumination. The effectiveness of vacuum annealing for enhancing TiO2 photochemical processes is demonstrated. The formation of oxygen in aqueous 1 M Na2SO4 electrolyte media (with/without chloride) is assessed using Clark probe measurements. Co-evolution of chlorine was evident in 1 M KCl. This work demonstrates that microwire photoelectrodes for woven form or brush structures are entirely feasible, and that pre-passivated titanium metal can be readily coated with titania nanocrystals via hydrothermal synthesis.

Spatial atomic layer deposition (sALD) of p-type SnO is demonstrated using a novel liquid ALD precursor, tin(II)-bis(tert-amyloxide), Sn(TAA) 2, and H 2O as the coreactant in a process which shows an increased deposition rate when compared to conventional temporal ALD. Compared to previously reported temporal ALD chemistries for the deposition of SnO, deposition rates of up to 19.5 times higher are obtained using Sn(TAA) 2 as a precursor in combination with atmospheric pressure sALD. Growths per cycle of 0.55 and 0.09 Å are measured at deposition temperatures of 100 and 210 °C, respectively. Common-gate thin film transistors (TFTs), fabricated using sALD with Sn(TAA) 2 result in linear mobilities of up to 0.4 cm 2 V –1 s –1 and on/off-current ratios, I On/I Off > 10 2. The combination of enhanced precursor chemistry and improved deposition hardware enables unprecedently high deposition rate ALD of p-type SnO, representing a significant step toward high-throughput p-type TFT fabrication on large area and flexible substrates.

In an attempt to tailor precursors for application in the deposition of phase pure SnO, we have evaluated a series of tin (1-6) ureide complexes. The complexes were successfully synthesized by employing N,N′-Trialkyl-functionalized ureide ligands, in which features such as stability, volatility, and decomposition could be modified with variation of the substituents on the ureide ligand in an attempt to find the complex with the ideal electronic, steric, or coordinative properties, which determine the fate of the final products. The tin(II) ureide complexes 1-6 were synthesized by direct reaction [Sn{NMe2}2] with aryl and alkyl isocyanates in a 1:2 molar ratio. All the complexes were characterized by NMR spectroscopy as well as elemental analysis and, where applicable, thermogravimetric (TG) analysis. The single-crystal X-ray diffraction studies of 2, 3, 4, and 6 revealed that the complexes crystallize in the monoclinic space group P2(1)/n (2 and 4) or in the triclinic space group P-1 (3 and 6) as monomers. Reaction with phenyl isocyanate results in the formation of the bimetallic species 5, which crystallizes in the triclinic space group P-1, a consequence of incomplete insertion into the Sn-NMe2 bonds, versus mesityl isocyanate, which produces a monomeric double insertion product, 6, under the same conditions, indicating a difference in reactivity between phenyl isocyanate and mesityl isocyanate with respect to insertion into Sn-NMe2 bonds. The metal centers in these complexes are all four-coordinate, displaying either distorted trigonal bipyramidal or trigonal bipyramidal geometries. The steric influence of the imido-ligand substituent has a clear effect on the coordination mode of the ureide ligands, with complexes 2 and 6, which contain the cyclohexyl and mesityl ligands, displaying κ2-O,N coordination modes, whereas κ2-N,N′ coordination modes are observed for the sterically bulkier tert-butyl and adamantyl derivatives, 3 and 4. The thermogravimetric analysis of the complexes 3 and 4 exhibited excellent physicochemical properties with clean single-step curves and low residual masses in their TG analyses suggesting their potential utility of these systems as MOCVD and ALD precursors.

We have successfully prepared and structurally characterized a family of eight tin(II) heteroleptic complexes, [Sn(NR2)(ON)]x (NR2 = NMe2 (1a–d) or N(SiMe3)2 (2a–d); x = 1 or 2) and four homoleptic systems, [Sn(κ2-ON)2] (3a–d) from a series of aminoalcohols and fluorinated aminoalcohols (H{ON}) having a different number of methyl/trifluoromethyl substituents at the α-carbon atom, [HOC(R1)(R2)CH2NMe2] (R1 = R2 = H (H{dmae}) (a); R1 = H, R2 = Me (H{dmap}) (b); R1 = R2 = Me (H{dmamp}) (c); R1 = R2 = CF3 (H{Fdmamp}) (d)). The synthetic route used reactions of either [Sn{N(SiMe3)2}2] or [Sn(NMe2)2] with one or two equivalents of the aminoalcohols (a–d) in dry aprotic solvents leading to elimination of amines and formation of the Sn(II) species 1a–d, 2a–d and 3a–d respectively. All complexes were thoroughly characterized by NMR spectroscopy (1H, 13C, 19F, and 119Sn) as well as single-crystal X-ray diffraction studies. In all case the solid state molecular structures of the complexes have been unambiguously established: the solid state structures 1a–b and 1c are dimeric with central {Sn2N2} cores resulting from bridging {μ2-NMe2} units, in which the Sn(II) atoms are four-coordinate. In contrast, the solid state structures of complexes 1c and 2a–c possess similarly dimeric structures, with four-coordinate Sn(II) atoms, in which the oxygen atoms of the {ON} ligand bridge two Sn(II) centres to form dimers with a central {Sn2O2} core. Uniquely in this study, 2d, [Sn(κ2-O,N-OCMe2CH2NMe2){N(SiMe3)2}] is monomeric with a three coordinate Sn(II) centre. The homoleptic complexes 3a–d are all isostructural with monomeric four-coordinate structures with disphenoidal geometries. Solution state NMR studies reveal complicated ligand exchange processes in the case of the heteroleptic complexes 1a–d and 2a–d. Contrastingly, the homoleptic systems 3a–d show no such behaviour. While complexes 1a–d and 2a–d displayed either poor thermal stability or multistep thermal decomposition processes, the thermal behaviour of the homoleptic complexes, 3a–d, was investigated in order to determine the effects, if any, of the degree of fluorination and asymmetry of the aminoalkoxide ligands on the suitability of these complexes as ALD precursors for the deposition of SnO thin films.

National statistical organizations often rely on non-exhaustive surveys to estimate industry-level production functions in years in which a full census is not conducted. When analyzing data from non-census years, we propose selecting an estimator based on a weighting of its in-sample and predictive performance. We compare Cobb–Douglas functional assumption to existing nonparametric shape constrained estimators and a newly proposed estimator. For simulated data, we find that our proposed estimator has the lowest weighted errors. Using the 2010 Chilean Annual National Industrial Survey, a Cobb–Douglas specification describes at least 90% as much variance as the best alternative estimators in practically all cases considered providing two insights: the benefits of using application data for selecting an estimator, and the benefits of structure in noisy data. Finally for the five largest manufacturing industries, we find that a 30% sample, on average, achieves 60% of the R-squared value that would have been achieved with a full census; however, the variance across industries and samples is large.

Late Cenozoic bivalve extinction in the North Atlantic area has been attributed to environmental deterioration. Within scallops and oysters – groups with a high growth rate – certain taxa which grew exceptionally fast became extinct, while others which grew slower survived. Those which grew exceptionally fast would have obtained protection from predators thereby, so their extinction may have been due to the detrimental effect of environmental change on growth rate and ability to avoid predation, rather than environmental change per se. We investigated some glycymeridid and carditid bivalves – groups with a low growth rate – to see whether extinct forms grew faster than extant forms. Extinct Glycymeris subovata grew at about the same rate as the slowest-growing living glycymeridid and much slower than late Cenozoic examples of extant G. americana, which grew at about the same rate as the fastest-growing living glycymeridid. Extinct G. obovata and extinct Cardites squamulosa ampla also grew slower than G. americana. These findings indicate that within bivalve groups with a low growth rate, extinction or survival of taxa through the late Cenozoic was not influenced by whether they were relatively fast or slow growers. By implication, environmental change acted directly to cause extinctions in these groups.

Various elements of the biota of the early Pliocene Coralline Crag Formation (southern North Sea Basin, eastern England) have been taken to indicate a warm temperate marine climate, with summer surface temperatures above 20 °C and winter temperatures above 10 °C [1]. However, summer and winter temperature estimates from oxygen-isotope (δ18O) sclerochronology of benthic invertebrates are typically in the respective cool temperate range when calculated using a plausible modelled value for water δ18O of +0.1‰. For instance, examples of the bivalve mollusc Aequipecten opercularis from the Ramsholt Member indicate summer maximum temperatures of 11.0–15.7 °C and winter minimum temperatures of 4.4–7.1 °C [2]. Amongst other evidence, the pattern of microgrowth-increment variation in Ramsholt-Member A. opercularis points to a depth below the summer thermocline, hence the temperatures recorded for that season provide an underestimate of surface temperature; this may well have been in the warm temperate summer range [2], as suggested by the pelagic dinoflagellate biota [3]. However, the cool temperate benthic winter temperatures indicated by isotopic data are likely also to have obtained at the surface, pointing to a greater seasonal range in surface temperature (perhaps > 15 °C) than in the modern North Sea (< 13 °C) [2]. This conclusion is not changed by adoption of a different (invariant) value for water δ18O and also follows from data for a specific late Pliocene interval (Mid-Piacenzian Warm Period) elsewhere in the southern North Sea Basin (Belgium, Netherlands [4]). Here we present isotopic evidence of a seasonal range in surface temperature higher than now at other times in the late Pliocene. Examples of A. opercularis from several horizons in the Lillo Formation (Belgium) and the Oosterhout Formation (Netherlands) indicate seasonal ranges in benthic temperature of 10–14 °C. Seasonal variation in water δ18O can only plausibly account for about 1 °C of these ranges. Taking into consideration microgrowth-increment evidence of a setting below the summer thermocline, the seafloor ranges imply that the surface seasonal range was sometimes 17 °C or more. Other bivalves (Atrina fragilis, Arctica islandica, Pygocardia rustica, Glycymeris radiolyrata) do not indicate such a high seasonal range in benthic (and hence surface) temperature but this can be attributed to inadequate sampling—time-averaging or a failure to recover evidence of seasonal extremes because of growth breaks. The high surface temperature range could reflect a reduction in vigour of the North Atlantic Current and hence diminished oceanic supply of heat in winter.References:[1] Vignols et al. (2019), Chem. Geol. 526, 62–83. https://doi.org/10.1016/j.chemgeo.2018.05.034.[2] Johnson et al. (2020), Palaeogeogr. Palaeoclimatol. Palaeoecol. 561. https://doi.org/10.1016/j.palaeo.2020.110046.[3] Head (1997), J. Paleontol. 71, 165–193. https://doi.org/10.1017/S0022336000039123.[4] Valentine et al. (2011), Palaeogeogr. Palaeoclimatol. Palaeoecol. 309, 9–16. https://doi.org/10.1016/j.palaeo.2011.05.015.

The shell δ18O of young modern Aequipecten opercularis from the southern North Sea provides an essentially faithful record of seasonal variation in seafloor temperature. In this well-mixed setting, A. opercularis shell δ18O also serves as a proxy for seasonal variation in surface temperature. Individuals from less agitated (e.g. deeper) settings in a warm climate would not be expected to record the full seasonal range in surface temperature because of thermal stratification in summer. Such circumstances have been invoked to explain cool isotopic summer temperatures from early Pliocene A. opercularis of eastern England. Support for a sub-thermocline setting derives from high-amplitude variation in microgrowth-increment size, which resembles the pattern in sub-thermocline A. opercularis from the southern Mediterranean Sea. Here, we present isotope and increment profiles from further sub-thermocline individuals, live-collected from a location in the Adriatic Sea for which we provide modelled values of expected shell δ18O. We also present data from supra-thermocline shells from the English Channel and French Mediterranean coast. The great majority of sub-thermocline A. opercularis show high-amplitude variation in increment size, and winter and summer δ18O values are generally quite close to expectation. However, the relatively warm summer conditions of 2015 are not recorded, in most cases due to a break in growth, perhaps caused by hypoxia. The supra-thermocline shells show subdued increment variation and yield isotopic winter and summer temperatures quite close to the local directly measured values. A. opercularis shells therefore provide a fairly good isotopic record of ambient temperature (if not always of relatively warm summer conditions below the thermocline) and their hydrographic setting can be determined from increment data. Early Pliocene examples from eastern England can be interpreted as having lived in a setting below the thermocline, with a higher seasonal range in surface temperature than now in the adjacent southern North Sea.

Halide perovskite solar cells containing a mixture of A-site cations are attracting considerable interest due to their improved stability and high power conversion efficiencies. Ionic transport is known to be an important predictor of perovskite behaviour, but the impact of partial A-site substitution on iodide ion diffusion is poorly understood. Here, we combine ab initio modelling, impedance spectroscopy and muon spin relaxation to investigate the effect on iodide ion transport of incorporating a low concentration of each of seven different sized cations (from small rubidium to large guanidinium) into methylammonium lead iodide. Experimental and simulation results are in good agreement, indicating that these cation substitutions increase the activation energy for iodide ion diffusion. We show for the first time that partial guanidinium substitution into methylammonium lead iodide strongly suppresses iodide ion transport. The insights gained from this multi-technique study are important for the future design of mixed-cation perovskite solar cells with enhanced performance.

SnO is a rare example of a stable p-type semiconductor material. Here, we describe the synthesis and characterisation of a family of Sn(ii) pyrrolide complexes for future application in the MOCVD and ALD of tin containing thin films. Reaction of the Sn(ii) amide complex, [{(Me3Si)2N}2Sn], with the N,N-bidentate pyrrole pro-ligand, L1H, forms the hetero- and homoleptic complexes [{L1}Sn{N(SiMe3)2}] (1) and [{L1}2Sn] (2), respectively, bearing the 2-dimethylaminomethyl-pyrrolide ligand (L1). Reaction of [{(Me3Si)2N)}2Sn] with the pyrrole-aldimine pro-ligands, L2H-L7H, results in the exclusive formation of the homoleptic bis-pyrrolide complexes [{L2-7}2Sn] (3-8). All complexes have been characterised by elemental analysis and NMR spectroscopy, and the molecular structures of complexes 1-5 and 8 are determined by single crystal X-ray diffraction. TG analysis and isothermal TG analysis have been used to evaluate the potential utility of these systems as MOCVD and ALD precursors.

Photoelectrochemical solar water splitting is a promising and sustainable technology for producing solar\ud fuels such as clean hydrogen from water. A widely studied photoanode semiconductor for this\ud application is TiO2, but it suffers from a large band gap (3.2 eV) and fast recombination of electrons and\ud holes. Herein, we present a novel, facile and rapid strategy to develop Mo-doped TiO2 (Mo:TiO2) mixed\ud anatase–rutile photoanodes using [Ti4Mo2O8(OEt)10]2 bimetallic oxo cages as a single source precursor.\ud These cages dissolved in tetrahydrofuran deposit by spray pyrolysis at 150 C forming films with\ud hierarchical porosity on the micrometer and nanometer scale. XPS, EDXS and UV-Vis spectroscopy\ud reveal Mo atoms evaporate during annealing in air at temperatures 650–800 C, contributing to the\ud formation of nanostructures and porosity. XPS depth profiling, XRD, EDXS, Raman, and electron\ud paramagnetic resonance indicate that the remaining Mo atoms are well spread and incorporated in the\ud TiO2 lattice, at interstitial or substitutional sites of the rutile or anatase phases depending on the\ud annealing temperature. Photocurrent measurements show that Mo:TiO2 photoanodes optimized at\ud 700 C outperform a TiO2 photoanode prepared in a similar manner by a factor of two at 1.23 VRHE.\ud Finally, UV-Vis spectroscopy, conduction and valence band calculations, and incident-to-photon\ud efficiency measurements show these Mo:TiO2 photoanodes possess a narrower band gap than TiO2 and\ud higher efficiency in the visible light range (5% at 400 nm). These outcomes open a new avenue in the\ud exploitation of titanium oxo cages and advance the development of photoelectrodes for water splitting\ud and energy applications

Understanding and quantifying the wake effect plays an important role in improving wind turbine designs and operations, as well as wind farm layout planning. The majority of the current wake effect...

We quantify the productive efficiency of a wind turbine, using power output and environmental variable data, measured either at the turbine or at a meteorological mast near the turbine. The methods described can potentially help with decision makings in asset procurement, maintenance planning, or wind turbine control optimization. The current recommendation from the International Electrotechnical Commission regarding turbine performance evaluation is to use a power curve or power coefficient. What is commonly used in practice is the average performance power curve or power coefficient. When using the power curve to quantify productive efficiency, one crucial shortcoming is the lack of a common best performance benchmark, while the power coefficient approach uses an absolute efficiency measure that is not achievable. We introduce a new approach for efficiency quantification based upon production economics' concepts which provides estimates of a best performance benchmark. Our specific approach has two main components: (a) a best performance power curve is estimated and used together with the average performance curve to show how well a turbine has performed relative to its full potential; and (b) a covariate matching procedure is developed to control for environmental influences for the comparison of turbine performances over different periods. Through a simulation study, we demonstrate that the proposed efficiency is more sensitive to potential changes in the turbine. When analyzing multi-year wind turbine data, we observe that the turbine's efficiency is improving during the first 2 years of operation and then remains relatively constant during years 3 and 4. Copyright © 2017 John Wiley & Sons, Ltd.

Tin sulphide (SnS) has attracted the attention of the photovoltaic (PV) community due to the combination of desirable optical properties, and its binary and earth abundant elemental composition, which should lead to relatively simple synthesis. However, currently the best SnS based PV device efficiency remains at 4.36%. Limited performance of this material is attributed to band gap alignment issues, deviations in doping concentration and poor film morphology. In this context Raman spectroscopy (RS) analysis can be useful as it facilitates the accurate evaluation of material properties. In this study we present a RS study, supported by X-ray diffraction and wavelength dispersive X-ray measurements, of α- and π-SnS thin films. In particular a complete description of SnS vibrational properties is made using six excitation wavelengths, including excitation energies coupled with certain optical band to band transitions, which leads to close to resonance measurement conditions. This study describes an in-depth analysis of the Raman spectra of both SnS structural polymorphs, including the differences in the number of observed peaks, with their relative intensities and Raman shift. Additionally, we evaluate the impact of low temperature heat treatment on SnS. These results explicitly present how the variation of the [S]/[Sn] ratio in samples deposited by different methods can lead to significant and correlated shifts in the relative positions of Raman peaks, which is only observed in the α-SnS phase. Furthermore, we discuss the suitability of using Raman spectroscopy based methodologies to extract fine stoichiometric variations in different α-SnS samples.

Yardstick competition is a regulation regime that forces local monopolies to compete against a variable cost or total cost benchmark. The variable cost benchmark ignores the fixed capital, creating a strong incentive to over-invest, whereas the total cost benchmark assumes all costs to be variable, ignoring the investment risk. We propose theoretical, methodological, and operational advances to increase applicability of yardstick competition in energy regulation. In the proposed conditional yardstick regime capital is treated as a fixed input, and the local monopolies compete against the variable cost conditional on the fixed input. We develop a benchmarking method that can handle multiple outputs, heterogeneity, and shape constraints to ensure incentive compatibility. We discuss the real-world application of the proposed regime to the Finnish electricity distribution firms in 2016-2023. We argue that smarter regulation of network industries can contribute to lower risk premiums and help to achieve win-win solutions both in terms of reliability and affordability.

WOS:000582677500029; International audience; Horizon scanning is an increasingly common strategy to identify key research needs and frame future agendas in science. Here, we present the results of the first such exercise for the field of sclerochronology, thereby providing an overview of persistent and emergent research questions that should be addressed by future studies. Through online correspondence following the 5th International Sclerochronology Conference in 2019, participants submitted and rated questions that addressed either knowledge gaps or promising applications of sclerochronology. An initial list of 130 questions was compiled based on contributions of conference attendees and reviewed by expert panels formed during the conference. Herein, we present and discuss the 50 questions rated to be of the highest priority, determined through an online survey distributed to sclerochronology community members post the conference. The final list (1) includes important questions related to mechanisms of biological control over biomineralization, (2) highlights state of the art applications of sclerochronological methods and data for solving long-standing questions in other fields such as climate science and ecology, and (3) emphasizes the need for common standards for data management and analysis. Although research priorities are continually reassessed, our list provides a roadmap that can be used to motivate research efforts and advance sclerochronology toward new, and more powerful, applications.

The taxonomic composition of the biota of the Coralline Crag Formation (early Pliocene, eastern England) provides conflicting evidence of seawater temperature during deposition, some taxa indicating cool temperate conditions by analogy with modern representatives or relatives, others warm temperate to subtropical/tropical conditions. Previous isotopic (δ18O) evidence of seasonal seafloor temperatures from serial ontogenetic sampling of bivalve mollusk shells indicated cool temperate winter (

Here we describe preliminary studies into the synthesis structural characterisation and thermal properties of a family of calcium xanthate precursors for application in the deposition of CaS thin films. The straightforward, low-temperature syntheses are detailed along with characterisation of the resulting compounds by 1H and 13C NMR and elemental analysis. Solid state molecular structures of all compounds, obtained from single-crystal X-ray diffraction, are presented and discussed in detail. The decomposition behaviour of the precursors has been probed through TGA, TGA-MS and thermal annealing experiments, indicating that the compounds decompose cleanly into CaS.