Solvothermal synthesis of one-dimensional chalcogenides containing group 13 elements

The solvothermal synthesis and characterisation of [C6H16N2][GaS2]2 (1), [C6H16N2][Ga2Se3(Se2)] (2), and mixed-metal phases with composition [C6H16N2][Ga2–xInxSe3(Se2)] (0 < x < 2)(3–5), is described. These materials have been characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis and UV/Vis diffuse reflectance spectroscopy. The materials contain one-dimensional anionic chains. In 1, these chains consist of edge-linked GaS4 tetrahedra, whilst in 2–5, the chains contain perselenide (Se2)2– units and comprise alternating four-membered [M2Se2] and five-membered [M2Se3] rings (where M = Ga, In). Compounds 3–5 represent the first examples of ternary mixed-metal [M2Se3(Se2)]2– chains.

Clouds, aerosols, and precipitation in the marine boundary layer: an ARM Mobile Facility Deployment

The Clouds, Aerosol, and Precipitation in the Marine Boundary Layer (CAP-MBL) deployment at Graciosa Island in the Azores generated a 21-month (April 2009–December 2010) comprehensive dataset documenting clouds, aerosols, and precipitation using the Atmospheric Radiation Measurement Program (ARM) Mobile Facility (AMF). The scientific aim of the deployment is to gain improved understanding of the interactions of clouds, aerosols, and precipitation in the marine boundary layer. Graciosa Island straddles the boundary between the subtropics and midlatitudes in the northeast Atlantic Ocean and consequently experiences a great diversity of meteorological and cloudiness conditions. Low clouds are the dominant cloud type, with stratocumulus and cumulus occurring regularly. Approximately half of all clouds contained precipitation detectable as radar echoes below the cloud base. Radar and satellite observations show that clouds with tops from 1 to 11 km contribute more or less equally to surface-measured precipitation at Graciosa. A wide range of aerosol conditions was sampled during the deployment consistent with the diversity of sources as indicated by back-trajectory analysis. Preliminary findings suggest important two-way interactions between aerosols and clouds at Graciosa, with aerosols affecting light precipitation and cloud radiative properties while being controlled in part by precipitation scavenging. The data from Graciosa are being compared with short-range forecasts made with a variety of models. A pilot analysis with two climate and two weather forecast models shows that they reproduce the observed time-varying vertical structure of lower-tropospheric cloud fairly well but the cloud-nucleating aerosol concentrations less well. The Graciosa site has been chosen to be a permanent fixed ARM site that became operational in October 2013.

The expression of the Cenomanian-Turonian oceanic anoxic event in Tibet

The Gongzha section of Tibet, China is located at the northern margin of the Indian Plate (SE Tethys) and is characterized by hemipelagic grey marls and marly limestones, light grey limestones and silty limestones, but no organic-rich sediments. High-resolution biostratigraphy reveals an expanded Cenomanian–Turonian (CT) boundary interval and the δ13C record includes the main features of the classical positive carbon-isotope excursion that characterizes the CT oceanic anoxic event. The biotic response inferred from the foraminifera suggests that oxic to dysoxic conditions prevailed, except for a short interval marked by peak abundance of Heterohelix that indicates a significantly dysoxic environment during the δ13C “b” peak excursion. The overall decreasing trend in redox-sensitive trace elements (RSTE) during the maximum δ13C excursion confirms the absence of significant longer-lasting anoxia in the Gongzha section. Enrichments in RSTE are linked to phases of increased detrital input. Chemical weathering indices suggest that the upper Cenomanian sediments accumulated under an increasingly hot and humid climate that culminated near the CT boundary. In the early Turonian lower weathering indices suggest a warm, drier climatic regime with reduced continental runoff. Phosphorus mass-accumulation rates show a significant peak at the onset of the positive δ13C excursion, followed by a decrease up to the basal Turonian. This pattern is positively correlated with the long-term decrease in detrital index as also observed in numerous other CT boundary sections (e.g., Eastbourne, Pueblo, and Whadi El Ghaib, Sinaï). Long-term phosphorus accumulation in the Gongzha section is therefore associated with changes in detrital input. The overall decreased detrital input can be explained by the increasingly remote continental sources due to the major transgression at the end of Cenomanian, coupled with changes in continental weathering intensity linked to increasingly more arid climate conditions.

Advances in understanding mineral dust and boundary layer processes over the Sahara from Fennec aircraft observations

The Fennec climate program aims to improve understanding of the Saharan climate system through a synergy of observations and modelling. We present a description of the Fennec airborne observations during 2011 and 2012 over the remote Sahara (Mauritania and Mali) and the advances in the understanding of mineral dust and boundary layer processes they have provided. Aircraft instrumentation aboard the UK FAAM BAe146 and French SAFIRE Falcon 20 is described, with specific focus on instrumentation specially developed and relevant to Saharan meteorology and dust. Flight locations, aims and associated meteorology are described. Examples and applications of aircraft measurements from the Fennec flights are presented, highlighting new scientific results delivered using a synergy of different instruments and aircraft. These include: (1) the first airborne measurement of dust particles sized up to 300 microns and associated dust fluxes in the Saharan atmospheric boundary layer (SABL), (2) dust uplift from the breakdown of the nocturnal low-level jet before becoming visible in SEVIRI satellite imagery, (3) vertical profiles of the unique vertical structure of turbulent fluxes in the SABL, (4) in-situ observations of processes in SABL clouds showing dust acting as CCN and IN at −15 °C, (5) dual-aircraft observations of the SABL dynamics, thermodynamics and composition in the Saharan heat low region (SHL), (6) airborne observations of a dust storm associated with a cold-pool (haboob) issued from deep convection over the Atlas, (7) the first airborne chemical composition measurements of dust in the SHL region with differing composition, sources (determined using Lagrangian backward trajectory calculations) and absorption properties between 2011 and 2012, (8) coincident ozone and dust surface area measurements suggest coarser particles provide a route for ozone depletion, (9) discrepancies between airborne coarse mode size distributions and AERONET sunphotometer retrievals under light dust loadings. These results provide insights into boundary layer and dust processes in the SHL region – a region of substantial global climatic importance.

Joint retrievals of cloud and drizzle in marine boundary layer clouds using ground-based radar, lidar and zenith radiances

Active remote sensing of marine boundary-layer clouds is challenging as drizzle drops often dominate the observed radar reflectivity. We present a new method to simultaneously retrieve cloud and drizzle vertical profiles in drizzling boundary-layer clouds using surface-based observations of radar reflectivity, lidar attenuated backscatter, and zenith radiances under conditions when precipitation does not reach the surface. Specifically, the vertical structure of droplet size and water content of both cloud and drizzle is characterised throughout the cloud. An ensemble optimal estimation approach provides full error statistics given the uncertainty in the observations. To evaluate the new method, we first perform retrievals using synthetic measurements from large-eddy simulation snapshots of cumulus under stratocumulus, where cloud water path is retrieved with an error of 31 g m−2 . The method also performs well in non-drizzling clouds where no assumption of the cloud profile is required. We then apply the method to observations of marine stratocumulus obtained during the Atmospheric Radiation Measurement MAGIC deployment in the Northeast Pacific. Here, retrieved cloud water path agrees well with independent three-channel microwave radiometer retrievals, with a root mean square difference of 10–20 g m−2.

Improving a global model from the boundary layer: total turbulent energy and the neutral limit Prandtl number

Model intercomparisons have identified important deficits in the representation of the stable boundary layer by turbulence parametrizations used in current weather and climate models. However, detrimental impacts of more realistic schemes on the large-scale flow have hindered progress in this area. Here we implement a total turbulent energy scheme into the climate model ECHAM6. The total turbulent energy scheme considers the effects of Earth’s rotation and static stability on the turbulence length scale. In contrast to the previously used turbulence scheme, the TTE scheme also implicitly represents entrainment flux in a dry convective boundary layer. Reducing the previously exaggerated surface drag in stable boundary layers indeed causes an increase in southern hemispheric zonal winds and large-scale pressure gradients beyond observed values. These biases can be largely removed by increasing the parametrized orographic drag. Reducing the neutral limit turbulent Prandtl number warms and moistens low-latitude boundary layers and acts to reduce longstanding radiation biases in the stratocumulus regions, the Southern Ocean and the equatorial cold tongue that are common to many climate models.

Advanced source apportionment of size-resolved trace elements at multiple sites in London during winter

Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.

CO2 emission estimation in the urban environment: measurement of the CO2 storage term

Eddy covariance has been used in urban areas to evaluate the net exchange of CO2 between the surface and the atmosphere. Typically, only the vertical flux is measured at a height 2–3 times that of the local roughness elements; however, under conditions of relatively low instability, CO2 may accumulate in the airspace below the measurement height. This can result in inaccurate emissions estimates if the accumulated CO2 drains away or is flushed upwards during thermal expansion of the boundary layer. Some studies apply a single height storage correction; however, this requires the assumption that the response of the CO2 concentration profile to forcing is constant with height. Here a full seasonal cycle (7th June 2012 to 3rd June 2013) of single height CO2 storage data calculated from concentrations measured at 10 Hz by open path gas analyser are compared to a data set calculated from a concurrent switched vertical profile measured (2 Hz, closed path gas analyser) at 10 heights within and above a street canyon in central London. The assumption required for the former storage determination is shown to be invalid. For approximately regular street canyons at least one other measurement is required. Continuous measurements at fewer locations are shown to be preferable to a spatially dense, switched profile, as temporal interpolation is ineffective. The majority of the spectral energy of the CO2 storage time series was found to be between 0.001 and 0.2 Hz (500 and 5 s respectively); however, sampling frequencies of 2 Hz and below still result in significantly lower CO2 storage values. An empirical method of correcting CO2 storage values from under-sampled time series is proposed.

Impact of Laptev Sea flaw polynyas on the atmospheric boundary layer and ice production using idealized mesoscale simulations

The interaction between polynyas and the atmospheric boundary layer is examined in the Laptev Sea using the regional, non-hydrostatic Consortium for Small-scale Modelling (COSMO) atmosphere model. A thermodynamic sea-ice model is used to consider the response of sea-ice surface temperature to idealized atmospheric forcing. The idealized regimes represent atmospheric conditions that are typical for the Laptev Sea region. Cold wintertime conditions are investigated with sea-ice–ocean temperature differences of up to 40 K. The Laptev Sea flaw polynyas strongly modify the atmospheric boundary layer. Convectively mixed layers reach heights of up to 1200 m above the polynyas with temperature anomalies of more than 5 K. Horizontal transport of heat expands to areas more than 500 km downstream of the polynyas. Strong wind regimes lead to a more shallow mixed layer with strong near-surface modifications, while weaker wind regimes show a deeper, well-mixed convective boundary layer. Shallow mesoscale circulations occur in the vicinity of ice-free and thin-ice covered polynyas. They are forced by large turbulent and radiative heat fluxes from the surface of up to 789 W m−2, strong low-level thermally induced convergence and cold air flow from the orographic structure of the Taimyr Peninsula in the western Laptev Sea region. Based on the surface energy balance we derive potential sea-ice production rates between 8 and 25 cm d−1. These production rates are mainly determined by whether the polynyas are ice-free or covered by thin ice and by the wind strength.

The BALTIMOS (BALTEX Integrated Model System) fi eld experiments: A comprehensive atmospheric boundary layer data set for model validation over the open and ice- covered Baltic Sea

A comprehensive atmospheric boundary layer (ABL) data set was collected in eight fi eld experiments (two during each season) over open water and sea ice in the Baltic Sea during 1998–2001 with the primary objective to validate the coupled atmospheric- ice-ocean-land surface model BALTIMOS (BALTEX Integrated Model System). Measurements were taken by aircraft, ships and surface stations and cover the mean and turbulent structure of the ABL including turbulent fl uxes, radiation fl uxes, and cloud conditions. Measurement examples of the spatial variability of the ABL over the ice edge zone and of the stable ABL over open water demonstrate the wide range of ABL conditions collected and the strength of the data set which can also be used to validate other regional models.

Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Ambient concentrations of trace elements with 2 h time resolution were measured in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM10–2.5 mass fraction, roughly twice that of the PM1.0–0.3 fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM10–2.5 sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.

Seasonality of submesoscale flows in the ocean surface boundary layer

A signature of submesoscale flows in the upper ocean is skewness in the distribution of relative vorticity. Expected to result for high Rossby-number flows, such skewness has implications for mixing, dissipation and stratification within the upper ocean. An array of moorings deployed in the Northeast Atlantic for one year as part of the OSMOSIS experiment reveals that relative vorticity is positively skewed during winter even though the scale of the Rossby number is less than 0.5. Furthermore, this skewness is reduced to zero during spring and autumn. There is also evidence of modest seasonal variations in the gradient Rossby number. The proposed mechanism by which relative vorticity is skewed is that the ratio of lateral to vertical buoyancy gradients, as summarized by the inverse gradient Richardson number, restricts its range during winter but less so at other times of the year. These results support recent observations and model simulations suggesting the upper ocean is host to a seasonal cycle in submesoscale turbulence.

Langmuir turbulence and surface heating in the ocean surface boundary layer

This study uses large-eddy simulation to investigate the structure of the ocean surface boundary layer (OSBL) in the presence of Langmuir turbulence and stabilizing surface heat fluxes. The OSBL consists of a weakly stratified layer, despite a surface heat flux, above a stratified thermocline. The weakly stratified (mixed) layer is maintained by a combination of a turbulent heat flux produced by the wave-driven Stokes drift and downgradient turbulent diffusion. The scaling of turbulence statistics, such as dissipation and vertical velocity variance, is only affected by the surface heat flux through changes in the mixed layer depth. Diagnostic models are proposed for the equilibrium boundary layer and mixed layer depths in the presence of surface heating. The models are a function of the initial mixed layer depth before heating is imposed and the Langmuir stability length. In the presence of radiative heating, the models are extended to account for the depth profile of the heating.