A step toward the wet surface chemistry of glycine and alanine on Cu{110}: destabilization and decomposition in the presence of near-ambient water vapor

The coadsorption of water with organic molecules under near-ambient pressure and temperature conditions opens up new reaction pathways on model catalyst surfaces that are not accessible in conventional ultrahigh-vacuum surfacescience experiments. The surface chemistry of glycine and alanine at the water-exposed Cu{110} interface was studied in situ using ambient-pressure photoemission and X-ray absorption spectroscopy techniques. At water pressures above 10-5 Torr a significant pressure-dependent decrease in the temperature for dissociative desorption was observed for both amino acids, accompanied by the appearance of a newCN intermediate, which is not observed for lower pressures. The most likely reaction mechanisms involve dehydrogenation induced by O and/or OH surface species resulting from the dissociative adsorption of water. The linear relationship between the inverse decomposition temperature and the logarithm of water pressure enables determination of the activation energy for the surface reaction, between 213 and 232 kJ/mol, and a prediction of the decomposition temperature at the solidliquid interface by extrapolating toward the equilibrium vapor pressure. Such experiments near the equilibrium vapor pressure provide important information about elementary surface processes at the solidliquid interface, which can be retrieved neither under ultrahigh vacuum conditions nor from interfaces immersed in a solution.

Processes controlling DOC in pore water during simulated drought cycles in six different UK peats

The effect of episodic drought on dissolved organic carbon (DOC) dynamics in peatlands has been the subject of considerable debate, as decomposition and DOC production is thought to increase under aerobic conditions, yet decreased DOC concentrations have been observed during drought periods. Decreased DOC solubility due to drought-induced acidification driven by sulphur (S) redox reactions has been proposed as a causal mechanism; however evidence is based on a limited number of studies carried out at a few sites. To test this hypothesis on a range of different peats, we carried out controlled drought simulation experiments on peat cores collected from six sites across Great Britain. Our data show a concurrent increase in sulphate (SO4) and a decrease in DOC across all sites during simulated water table draw-down, although the magnitude of the relationship between SO4 and DOC differed between sites. Instead, we found a consistent relationship across all sites between DOC decrease and acidification measured by the pore water acid neutralising capacity (ANC). ANC provided a more consistent measure of drought-induced acidification than SO4 alone because it accounts for differences in base cation and acid anions concentrations between sites. Rewetting resulted in rapid DOC increases without a concurrent increase in soil respiration, suggesting DOC changes were primarily controlled by soil acidity not soil biota. These results highlight the need for an integrated analysis of hydrologically driven chemical and biological processes in peatlands to improve our understanding and ability to predict the interaction between atmospheric pollution and changing climatic conditions from plot to regional and global scales.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

An analysis of long-term trends, seasonality and short-term dynamics in water quality data from Plynlimon, Wales

This paper examines two hydrochemical time-series derived from stream samples taken in the Upper Hafren catchment, Plynlimon, Wales. One time-series comprises data collected at 7-hour intervals over 22 months (Neal et al., submitted, this issue), while the other is based on weekly sampling over 20 years. A subset of determinands: aluminium, calcium, chloride, conductivity, dissolved organic carbon, iron, nitrate, pH, silicon and sulphate are examined within a framework of non-stationary time-series analysis to identify determinand trends, seasonality and short-term dynamics. The results demonstrate that both long-term and high-frequency monitoring provide valuable and unique insights into the hydrochemistry of a catchment. The long-term data allowed analysis of long-termtrends, demonstrating continued increases in DOC concentrations accompanied by declining SO4 concentrations within the stream, and provided new insights into the changing amplitude and phase of the seasonality of the determinands such as DOC and Al. Additionally, these data proved invaluable for placing the short-term variability demonstrated within the high-frequency data within context. The 7-hour data highlighted complex diurnal cycles for NO3, Ca and Fe with cycles displaying changes in phase and amplitude on a seasonal basis. The high-frequency data also demonstrated the need to consider the impact that the time of sample collection can have on the summary statistics of the data and also that sampling during the hours of darkness provides additional hydrochemical information for determinands which exhibit pronounced diurnal variability. Moving forward, this research demonstrates the need for both long-term and high-frequency monitoring to facilitate a full and accurate understanding of catchment hydrochemical dynamics.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KMGAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KMGAP is based on the PRA model framework (P¨oschl-Rudich- Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270K is close to unity (Winkler et al., 2006). Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.

Acidity controls on dissolved organic carbon mobility in organic soils

Dissolved organic carbon (DOC) concentrations in surface waters have increased across much of Europe and North America, with implications for the terrestrial carbon balance, aquatic ecosystem functioning, water treatment costs and human health. Over the past decade, many hypotheses have been put forward to explain this phenomenon, from changing climate and land-management to eutrophication and acid deposition. Resolution of this debate has been hindered by a reliance on correlative analyses of time-series data, and a lack of robust experimental testing of proposed mechanisms. In a four-year, four-site replicated field experiment involving both acidifying and de-acidifying treatments, we tested the hypothesis that DOC leaching was previously suppressed by high levels of soil acidity in peat and organo-mineral soils, and therefore that observed DOC increases a consequence of decreasing soil acidity. We observed a consistent, positive relationship between DOC and acidity change at all sites. Responses were described by similar hyperbolic relationships between standardised changes in DOC and hydrogen ion concentrations at all sites, suggesting potentially general applicability. These relationships explained a substantial proportion of observed changes in peak DOC concentrations in nearby monitoring streams, and application to a UK-wide upland soil pH dataset suggests that recovery from acidification alone could have led to soil solution DOC increases in the range 46-126% by habitat type since 1978. Our findings raise the possibility that changing soil acidity may have wider impacts on ecosystem carbon balances. Decreasing sulphur deposition may be accelerating terrestrial carbon loss, and returning surface waters to a natural, high-DOC condition.

Water quality trends in the Windrush catchment: Nitrogen speciation and sediment interactions

For the predominantly agricultural River Windrush catchment, spatial variations in concentrations of nitrogen species and suspended sediment were strongly related to geology and land use. Temporal patterns of NO3- and NO2- concentrations during the three year study were highly correlated with seasonal variations in baseflow. Suspended sediment concentrations were mainly controlled by storm discharge. Variations in total ammonium concentrations reflected both flow controls. Suspended sediment effects total ammonium and organic nitrogen transport to the aquatic system, and in-stream cycling processes. Organic nitrogen did not display consistent seasonal variations, but concentrations occasionally exceeding those of NO3-. Overall, NO3- and organic nitrogen were the most important at 60% and -40%, of total nitrogen load, respectively. Future assessments of agriculture impact on river water quality should consider the total nitrogen load, and not solely that of NO3-.

Contribution of N Species and P Fractions to Stream Water Quality in Agricultural Catchments

The contribution from agricultural catchments to stream nitrogen and phosphorus concentrations was assessed by evaluation of the chemical composition of these nutrients in agricultural runoff for both surface and subsurface flow pathways. A range of land uses (grazed and ungrazed grassland, cereals, roots) in intensive agricultural systems was studied at scales from hillslope plots (0.5m2) to large catchment (>300km2). By fractionating the total nutrient load it was possible to establish that most of the phosphorus was transported in the unreactive (particulate and organic) fraction via surface runoff. This was true regardless of the scale of measurement. The form of the nitrogen load varied with land use and grazing intensity. High loads of dissolved inorganic nitrogen (with >90% transported as NH4-N) were recorded in surface runoff from heavily grazed land. In subsurface flow from small (2km2) subcatchments and in larger (>300 km2) catchments, organic nitrogen was found to be an important secondary constituent of the total nitrogen load, comprising 40% of the total annual load.

An unusual axial–axial combination of alternating cyclic rings in the chair conformations of hexameric water and chlorine-water clusters

An alternating hexameric water (H2O)(6) cluster and a chlorine-water cluster [Cl-2(H2O)(4)](2-) in the chair forms combine axially to each other to form a 1D chain [{Cl-2(H2O)(6)}(2-)](n) in complex [FeL2]Cl center dot(H2O)(3) (L=2-[(2-methylaminoethylimino)-methyl]-phenol)]. The water molecules display extensive H-bonding interactions with monomeric iron-organic units to form a hydrogen-bonded 2D supramolecular assembly.

Water-soluble tripeptide Aβ (9−11) forms amyloid-Like fibrils and exhibits neurotoxicity

A water-soluble, hydrophilic tripeptide GYE, having sequence identity with the N-terminal segment of amyloid peptides A�(9-11), upon selfassociation exhibits amyloid-like fibrils and significant neurotoxicity towards the Neuro2A cell line. However, the tripeptides GFE and GWE, in which the centrally located tyrosine residue has been replaced by phenylalanine or tryptophan, fail to show amyloidogenic behavior and exhibit little or no neurotoxicity.

Eemian and Holocene sea-surface conditions in the southern Black Sea: organic-walled dinoflagellate cyst record from core 22-GC3/3

In order to compare the sea-surface conditions in the Black Sea during the Holocene and Eemian, sapropelic parts of marine core 22-GC3 (42°13.53′N/36°29.55′E, 838 m water depth) were studied for organic-walled dinoflagellate cyst content. The record shows a change from freshwater/brackish assemblages (Pyxidinopsis psilata, Spiniferites cruciformis, and Caspidinium rugosum) to more marine assemblages (Lingulodinium machaerophorum and Spiniferites ramosus complex) during each interglacial, due to the inflow of saline Mediterranean water. The lacustrine–marine transitions in 22-GC3 occurred at ~ 8.3 cal kyr BP during the early Holocene and ~ 128 kyr BP during the early Eemian, slightly later compared to the onset of interglacial conditions on the adjacent land. Dinoflagellate cyst assemblages reveal higher sea-surface salinity (~ 28–30) (e.g. Spiniferites pachydermus, Bitectatodinium tepikiense, and Spiniferites mirabilis) around ~ 126.5–121 kyr BP in comparison to the Holocene (~ 15–20) as well as relatively high sea-surface temperature (e.g. Tuberculodinium vancampoae, S. pachydermus, and S. mirabilis) especially at ~ 127.6–125.3 kyr BP. Establishment of high sea-surface salinity during the Eemian correlates very well with reconstructed relatively high global sea-level and is explained as a combined effect of increased Mediterranean supply and high temperatures at the beginning of the last interglacial. The observed changes in the dinocyst record highlight the importance of nutrients for the composition of the Eemian and Holocene dinocyst assemblages.

Climate responses to anthropogenic emissions of short-lived climate pollutants

Policies to control air quality focus on mitigating emissions of aerosols and their precursors, and other short-lived climate pollutants (SLCPs). On a local scale, these policies will have beneficial impacts on health and crop yields, by reducing particulate matter (PM) and surface ozone concentrations; however, the climate impacts of reducing emissions of SLCPs are less straightforward to predict. In this paper we consider a set of idealised, extreme mitigation strategies, in which the total anthropogenic emissions of individual SLCP emissions species are removed. This provides an upper bound on the potential climate impacts of such air quality strategies. We focus on evaluating the climate responses to changes in anthropogenic emissions of aerosol precursor species: black carbon (BC), organic carbon (OC) and sulphur dioxide (SO2). We perform climate integrations with four fully coupled atmosphere-ocean global climate models (AOGCMs), and examine the effects on global and regional climate of removing the total land-based anthropogenic emissions of each of the three aerosol precursor species. We find that the SO2 emissions reductions lead to the strongest response, with all three models showing an increase in surface temperature focussed in the northern hemisphere high latitudes, and a corresponding increase in global mean precipitation and run-off. Changes in precipitation and run-off patterns are driven mostly by a northward shift in the ITCZ, consistent with the hemispherically asymmetric warming pattern driven by the emissions changes. The BC and OC emissions reductions give a much weaker forcing signal, and there is some disagreement between models in the sign of the climate responses to these perturbations. These differences between models are due largely to natural variability in sea-ice extent, circulation patterns and cloud changes. This large natural variability component to the signal when the ocean circulation and sea-ice are free-running means that the BC and OC mitigation measures do not necessarily lead to a discernible climate response.

Evaluation of optical techniques for characterising soil organic matter quality in agricultural soils

Soil organic matter (SOM) is one of the main global carbon pools. It is a measure of soil quality as its presence increases carbon sequestration and improves physical and chemical soil properties. The determination and characterisation of humic substances gives essential information of the maturity and stresses of soils as well as of their health. However, the determination of the exact nature and molecular structure of these substances has been proven difficult. Several complex techniques exist to characterise SOM and mineralisation and humification processes. One of the more widely accepted for its accuracy is nuclear magnetic resonance (NMR) spectroscopy. Despite its efficacy, NMR needs significant economic resources, equipment, material and time. Proxy measures like the fluorescence index (FI), cold and hot-water extractable carbon (CWC and HWC) and SUVA-254 have the potential to characterise SOM and, in combination, provide qualitative and quantitative data of SOM and its processes. Spanish and British agricultural cambisols were used to measure SOM quality and determine whether similarities were found between optical techniques and 1H NMR results in these two regions with contrasting climatic conditions. High correlations (p < 0.001) were found between the specific aromatic fraction measured with 1H NMR and SUVA-254 (Rs = 0.95) and HWC (Rs = 0.90), which could be described using a linear model. A high correlation between FI and the aromatics fraction measured with 1H NMR (Rs = −0.976) was also observed. In view of our results, optical measures have a potential, in combination, to predict the aromatic fraction of SOM without the need of expensive and time consuming techniques.

Evaluating the climate and air quality impacts of short-lived pollutants

This paper presents a summary of the work done within the European Union's Seventh Framework Programme project ECLIPSE (Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants). ECLIPSE had a unique systematic concept for designing a realistic and effective mitigation scenario for short-lived climate pollutants (SLCPs; methane, aerosols and ozone, and their precursor species) and quantifying its climate and air quality impacts, and this paper presents the results in the context of this overarching strategy. The first step in ECLIPSE was to create a new emission inventory based on current legislation (CLE) for the recent past and until 2050. Substantial progress compared to previous work was made by including previously unaccounted types of sources such as flaring of gas associated with oil production, and wick lamps. These emission data were used for present-day reference simulations with four advanced Earth system models (ESMs) and six chemistry transport models (CTMs). The model simulations were compared with a variety of ground-based and satellite observational data sets from Asia, Europe and the Arctic. It was found that the models still underestimate the measured seasonality of aerosols in the Arctic but to a lesser extent than in previous studies. Problems likely related to the emissions were identified for northern Russia and India, in particular. To estimate the climate impacts of SLCPs, ECLIPSE followed two paths of research: the first path calculated radiative forcing (RF) values for a large matrix of SLCP species emissions, for different seasons and regions independently. Based on these RF calculations, the Global Temperature change Potential metric for a time horizon of 20 years (GTP20) was calculated for each SLCP emission type. This climate metric was then used in an integrated assessment model to identify all emission mitigation measures with a beneficial air quality and short-term (20-year) climate impact. These measures together defined a SLCP mitigation (MIT) scenario. Compared to CLE, the MIT scenario would reduce global methane (CH4) and black carbon (BC) emissions by about 50 and 80 %, respectively. For CH4, measures on shale gas production, waste management and coal mines were most important. For non-CH4 SLCPs, elimination of high-emitting vehicles and wick lamps, as well as reducing emissions from gas flaring, coal and biomass stoves, agricultural waste, solvents and diesel engines were most important. These measures lead to large reductions in calculated surface concentrations of ozone and particulate matter. We estimate that in the EU, the loss of statistical life expectancy due to air pollution was 7.5 months in 2010, which will be reduced to 5.2 months by 2030 in the CLE scenario. The MIT scenario would reduce this value by another 0.9 to 4.3 months. Substantially larger reductions due to the mitigation are found for China (1.8 months) and India (11–12 months). The climate metrics cannot fully quantify the climate response. Therefore, a second research path was taken. Transient climate ensemble simulations with the four ESMs were run for the CLE and MIT scenarios, to determine the climate impacts of the mitigation. In these simulations, the CLE scenario resulted in a surface temperature increase of 0.70 ± 0.14 K between the years 2006 and 2050. For the decade 2041–2050, the warming was reduced by 0.22 ± 0.07 K in the MIT scenario, and this result was in almost exact agreement with the response calculated based on the emission metrics (reduced warming of 0.22 ± 0.09 K). The metrics calculations suggest that non-CH4 SLCPs contribute ~ 22 % to this response and CH4 78 %. This could not be fully confirmed by the transient simulations, which attributed about 90 % of the temperature response to CH4 reductions. Attribution of the observed temperature response to non-CH4 SLCP emission reductions and BC specifically is hampered in the transient simulations by small forcing and co-emitted species of the emission basket chosen. Nevertheless, an important conclusion is that our mitigation basket as a whole would lead to clear benefits for both air quality and climate. The climate response from BC reductions in our study is smaller than reported previously, possibly because our study is one of the first to use fully coupled climate models, where unforced variability and sea ice responses cause relatively strong temperature fluctuations that may counteract (and, thus, mask) the impacts of small emission reductions. The temperature responses to the mitigation were generally stronger over the continents than over the oceans, and with a warming reduction of 0.44 K (0.39–0.49) K the largest over the Arctic. Our calculations suggest particularly beneficial climate responses in southern Europe, where surface warming was reduced by about 0.3 K and precipitation rates were increased by about 15 (6–21) mm yr−1 (more than 4 % of total precipitation) from spring to autumn. Thus, the mitigation could help to alleviate expected future drought and water shortages in the Mediterranean area. We also report other important results of the ECLIPSE project.

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.