Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

Airborne measurements of the spatial distribution of aerosol chemical composition across Europe and evolution of the organic fraction

The spatial distribution of aerosol chemical composition and the evolution of the Organic Aerosol (OA) fraction is investigated based upon airborne measurements of aerosol chemical composition in the planetary boundary layer across Europe. Sub-micron aerosol chemical composition was measured using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). A range of sampling conditions were evaluated, including relatively clean background conditions, polluted conditions in North-Western Europe and the near-field to far-field outflow from such conditions. Ammonium nitrate and OA were found to be the dominant chemical components of the sub-micron aerosol burden, with mass fractions ranging from 20--50% each. Ammonium nitrate was found to dominate in North-Western Europe during episodes of high pollution, reflecting the enhanced NO_x and ammonia sources in this region. OA was ubiquitous across Europe and concentrations generally exceeded sulphate by 30--160%. A factor analysis of the OA burden was performed in order to probe the evolution across this large range of spatial and temporal scales. Two separate Oxygenated Organic Aerosol (OOA) components were identified; one representing an aged-OOA, termed Low Volatility-OOA and another representing fresher-OOA, termed Semi Volatile-OOA on the basis of their mass spectral similarity to previous studies. The factors derived from different flights were not chemically the same but rather reflect the range of OA composition sampled during a particular flight. Significant chemical processing of the OA was observed downwind of major sources in North-Western Europe, with the LV-OOA component becoming increasingly dominant as the distance from source and photochemical processing increased. The measurements suggest that the aging of OA can be viewed as a continuum, with a progression from a less oxidised, semi-volatile component to a highly oxidised, less-volatile component. Substantial amounts of pollution were observed far downwind of continental Europe, with OA and ammonium nitrate being the major constituents of the sub-micron aerosol burden. Such anthropogenically perturbed air masses can significantly perturb regional climate far downwind of major source regions.

Doppler lidar measurements of oriented planar ice crystals falling from supercooled and glaciated layer clouds

The properties of planar ice crystals settling horizontally have been investigated using a vertically pointing Doppler lidar. Strong specular reflections were observed from their oriented basal facets, identified by comparison with a second lidar pointing 4° from zenith. Analysis of 17 months of continuous high-resolution observations reveals that these pristine crystals are frequently observed in ice falling from mid-level mixed-phase layer clouds (85% of the time for layers at −15 °C). Detailed analysis of a case study indicates that the crystals are nucleated and grow rapidly within the supercooled layer, then fall out, forming well-defined layers of specular reflection. From the lidar alone the fraction of oriented crystals cannot be quantified, but polarimetric radar measurements confirmed that a substantial fraction of the crystal population was well oriented. As the crystals fall into subsaturated air, specular reflection is observed to switch off as the crystal faces become rounded and lose their faceted structure. Specular reflection in ice falling from supercooled layers colder than −22 °C was also observed, but this was much less pronounced than at warmer temperatures: we suggest that in cold clouds it is the small droplets in the distribution that freeze into plates and produce specular reflection, whilst larger droplets freeze into complex polycrystals. The lidar Doppler measurements show that typical fall speeds for the oriented crystals are ≈ 0.3 m s−1, with a weak temperature correlation; the corresponding Reynolds number is Re ∼ 10, in agreement with light-pillar measurements. Coincident Doppler radar observations show no correlation between the specular enhancement and the eddy dissipation rate, indicating that turbulence does not control crystal orientation in these clouds. Copyright © 2010 Royal Meteorological Society

Climate change and the flowering time of annual crops

Crop production is inherently sensitive to variability in climate. Temperature is a major determinant of the rate of plant development and, under climate change, warmer temperatures that shorten development stages of determinate crops will most probably reduce the yield of a given variety. Earlier crop flowering and maturity have been observed and documented in recent decades, and these are often associated with warmer (spring) temperatures. However, farm management practices have also changed and the attribution of observed changes in phenology to climate change per se is difficult. Increases in atmospheric [CO2] often advance the time of flowering by a few days, but measurements in FACE (free air CO2 enrichment) field-based experiments suggest that elevated [CO2] has little or no effect on the rate of development other than small advances in development associated with a warmer canopy temperature. The rate of development (inverse of the duration from sowing to flowering) is largely determined by responses to temperature and photoperiod, and the effects of temperature and of photoperiod at optimum and suboptimum temperatures can be quantified and predicted. However, responses to temperature, and more particularly photoperiod, at supraoptimal temperature are not well understood. Analysis of a comprehensive data set of time to tassel initiation in maize (Zea mays) with a wide range of photoperiods above and below the optimum suggests that photoperiod modulates the negative effects of temperature above the optimum. A simulation analysis of the effects of prescribed increases in temperature (0-6 degrees C in + 1 degrees C steps) and temperature variability (0% and + 50%) on days to tassel initiation showed that tassel initiation occurs later, and variability was increased, as the temperature exceeds the optimum in models both with and without photoperiod sensitivity. However, the inclusion of photoperiod sensitivity above the optimum temperature resulted in a higher apparent optimum temperature and less variability in the time of tassel initiation. Given the importance of changes in plant development for crop yield under climate change, the effects of photoperiod and temperature on development rates above the optimum temperature clearly merit further research, and some of the knowledge gaps are identified herein.

Pre-pubertal measurements of the somatotrophic axis as predictors of milk production in Holstein-Friesian dairy cows

This study investigated possible relationships between measurements of the somatotrophic axis in pre-pubertal dairy calves and subsequent milk yields. Endogenous growth hormone (GH) release was measured through a fed and fasted period in fifty 6-month-old Holstein-Friesian heifers and they were then challenged with growth hormone-releasing factor (GRF) to assess their GH release pattern. Insulin-like growth factor-I (IGF-I), insulin and glucose concentrations were measured in relation to time of feeding. Cows were subsequently monitored through their first three lactations to record peak and 305-day milk yields. In the first lactation, milk energy output for the first 120 days of lactation was also calculated. The mean 305-day milk yield increased from 7417 +/- 191 kg in the first lactation (n = 37) to 8749 +/- 252 kg in the third (n = 25). There were no significant relationships between any measures of GH secretion and peak or 305-day yield in any lactation. A highly significant positive relationship was established between the GH peak measured 10 min post-GRF challenge and 120-day milk energy values in the first lactation. This relationship was, however, only present in the subpopulation of 12 cows culled after one or two lactations and was absent in the 25 animals remaining for the third lactation. There were no significant relationships between pre-pubertal IGF-I and fed or fasted insulin or glucose concentrations and any subsequent measurement of yield. The usefulness of GH secretagogue challenges in calves as a predictive test for future milk production is thus limited but may have some bearing on nutrient partitioning and longevity. (c) 2005 Elsevier Inc. All rights reserved.

Time-resolved gas-phase kinetic and quantum chemical studies of reactions of silylene with chlorine-containing species. 1. HCl

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with HCL The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas, at five temperatures in the range of 296-611 K. The second-order rate constants fitted the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.51 +/- 0.06) + (1.92 +/- 0.47 kJ mol(-1))/RTIn10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range of 10-100 Torr, but showed small decreases in value of no more than 20% ( +/- 10%) at I Toff, at both the highest and lowest temperatures. The data are consistent with formation of an initial weakly bound donor-acceptor complex, which reacts by two parallel pathways. The first is by chlorine-to-silicon H-shift to make vibrationally excited chlorosilane, SiH3Cl*, which yields HSiCl by H-2 elimination from silicon. In the second pathway, the complex proceeds via H-2 elimination (4-center process) to make chlorosilylene, HSiCl, directly. This interpretation is supported by ab initio quantum calculations carried out at the G3 level which reveal the direct H-2 elimination route for the first time. RRKM modeling predicts the approximate magnitude of the pressure effect but is unable to determine the proportions of each pathway. The experimental data agree with the only previous measurements at room temperature. Comparisons with other reactions of SiH2 are also drawn.

Solvent influences on metastable polymorph lifetimes: real-time interconversions using energy dispersive X-ray diffractometry

Solvent influences on the crystallization of polymorph and hydrate forms of the nootropic drug piracetam (2-oxo-pyrrolidineacetamide) were investigated from water, methanol, 2-propanol, isobutanol, and nitromethane. Crystal growth profiles of piracetam polymorphs were constructed using time-resolved diffraction snapshots collected for each solvent system. Measurements were performed by in situ energy dispersive X-ray diffraction recorded in Station 16.4 at the synchrotron radiation source (SRS) at Daresbury Laboratory, CCLRC UK. Crystallizations from methanol, 2-propanol, isobutanol, and nitromethane progressed in a similar fashion with the initial formation of form I which then converted relatively quickly to form II with form III being generated upon further cooling. However, considerable differences were observed for the polymorphs lifetime and both the rate and temperature of conversion using the different solvents. The thermodynamically unstable form I was kinetically favored in isobutanol and nitromethane where traces of this polymorph were observed below 10 degrees C. In contrast, the transformation of form II and subsequent growth of form III were inhibited in 2-propanol and nitromethane solutions. Aqueous solutions produced hydrate forms of piracetam which are different from the reported monohydrate; this crystallization evolved through successive generation of transient structures which transformed upon exchange of intramolecular water between the liquid and crystalline phases. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 96:1069-1078, 2007.

Using continuous ground-based radar and lidar measurements for evaluating the representation of clouds in four operational models

The ability of four operational weather forecast models [ECMWF, Action de Recherche Petite Echelle Grande Echelle model (ARPEGE), Regional Atmospheric Climate Model (RACMO), and Met Office] to generate a cloud at the right location and time (the cloud frequency of occurrence) is assessed in the present paper using a two-year time series of observations collected by profiling ground-based active remote sensors (cloud radar and lidar) located at three different sites in western Europe (Cabauw. Netherlands; Chilbolton, United Kingdom; and Palaiseau, France). Particular attention is given to potential biases that may arise from instrumentation differences (especially sensitivity) from one site to another and intermittent sampling. In a second step the statistical properties of the cloud variables involved in most advanced cloud schemes of numerical weather forecast models (ice water content and cloud fraction) are characterized and compared with their counterparts in the models. The two years of observations are first considered as a whole in order to evaluate the accuracy of the statistical representation of the cloud variables in each model. It is shown that all models tend to produce too many high-level clouds, with too-high cloud fraction and ice water content. The midlevel and low-level cloud occurrence is also generally overestimated, with too-low cloud fraction but a correct ice water content. The dataset is then divided into seasons to evaluate the potential of the models to generate different cloud situations in response to different large-scale forcings. Strong variations in cloud occurrence are found in the observations from one season to the same season the following year as well as in the seasonal cycle. Overall, the model biases observed using the whole dataset are still found at seasonal scale, but the models generally manage to well reproduce the observed seasonal variations in cloud occurrence. Overall, models do not generate the same cloud fraction distributions and these distributions do not agree with the observations. Another general conclusion is that the use of continuous ground-based radar and lidar observations is definitely a powerful tool for evaluating model cloud schemes and for a responsive assessment of the benefit achieved by changing or tuning a model cloud

A method for estimating the turbulent kinetic energy dissipation rate from a vertically pointing Doppler lidar, and independent evaluation from balloon-borne in situ measurements

A method of estimating dissipation rates from a vertically pointing Doppler lidar with high temporal and spatial resolution has been evaluated by comparison with independent measurements derived from a balloon-borne sonic anemometer. This method utilizes the variance of the mean Doppler velocity from a number of sequential samples and requires an estimate of the horizontal wind speed. The noise contribution to the variance can be estimated from the observed signal-to-noise ratio and removed where appropriate. The relative size of the noise variance to the observed variance provides a measure of the confidence in the retrieval. Comparison with in situ dissipation rates derived from the balloon-borne sonic anemometer reveal that this particular Doppler lidar is capable of retrieving dissipation rates over a range of at least three orders of magnitude. This method is most suitable for retrieval of dissipation rates within the convective well-mixed boundary layer where the scales of motion that the Doppler lidar probes remain well within the inertial subrange. Caution must be applied when estimating dissipation rates in more quiescent conditions. For the particular Doppler lidar described here, the selection of suitably short integration times will permit this method to be applicable in such situations but at the expense of accuracy in the Doppler velocity estimates. The two case studies presented here suggest that, with profiles every 4 s, reliable estimates of ϵ can be derived to within at least an order of magnitude throughout almost all of the lowest 2 km and, in the convective boundary layer, to within 50%. Increasing the integration time for individual profiles to 30 s can improve the accuracy substantially but potentially confines retrievals to within the convective boundary layer. Therefore, optimization of certain instrument parameters may be required for specific implementations.

Principles and calibration of solid phase microextraction fibre (passive sampler) for measurements of airflow and air infiltration in dwellings

Tracer gas techniques have been the most appropriate experimental method of determining airflows and ventilation rates in houses. However, current trends to reduce greenhouse gas effects have prompted the need for alternative techniques, such as passive sampling. In this research passive sampling techniques have been used to demonstrate the potential to fulfil these requirements by using solutions of volatile organic compounds (VOCs) and solid phase microextraction (SPME) fibres. These passive sampling techniques have been calibrated against tracer gas decay techniques and measurements from a standard orifice plate. Two constant sources of volatile organic compounds were diffused into two sections of a humidity chamber and sampled using SPME fibres. From a total of four SPME fibres (two in each section), reproducible results were obtained. Emission rates and air movement from one section to the other were predicted using developed algorithms. Comparison of the SPME fibre technique with that of the tracer gas technique and measurements from an orifice plate showed similar results with good precision and accuracy. With these fibres, infiltration rates can be measured over grab samples in a time weighted averaged period lasting from 10 minutes up to several days. Key words: passive samplers, solid phase microextraction fibre, tracer gas techniques, airflow, air infiltration, houses.

Variability in surface atmospheric electric field measurements

An electrical current of the order one picoamp per metre squared flows vertically in the Earth's atmosphere, between the ionosphere at approximately 50km altitude and the surface. This current is generated by global thunderstorm activity and is modulated by galactic cosmic rays and atmospheric aerosol. In fair weather conditions, this current cause a vertical atmospheric electric field, commonly measured as a potential gradient. For circumstances other than fair weather conditions, the potential gradient varies, from small steady enhancements in fog to large fluctuations in thunderstorms. The atmospheric potential gradient is continuously monitored at the Reading University Atmospheric Observatory. An account of the variability of the potential gradient on a variety of time scales will be presented.

Remote sensing of cloud properties using ground-based measurements of zenith radiance

We have conducted the first extensive field test of two new methods to retrieve optical properties for overhead clouds that range from patchy to overcast. The methods use measurements of zenith radiance at 673 and 870 nm wavelengths and require the presence of green vegetation in the surrounding area. The test was conducted at the Atmospheric Radiation Measurement Program Oklahoma site during September–November 2004. These methods work because at 673 nm (red) and 870 nm (near infrared (NIR)), clouds have nearly identical optical properties, while vegetated surfaces reflect quite differently. The first method, dubbed REDvsNIR, retrieves not only cloud optical depth τ but also radiative cloud fraction. Because of the 1-s time resolution of our radiance measurements, we are able for the first time to capture changes in cloud optical properties at the natural timescale of cloud evolution. We compared values of τ retrieved by REDvsNIR to those retrieved from downward shortwave fluxes and from microwave brightness temperatures. The flux method generally underestimates τ relative to the REDvsNIR method. Even for overcast but inhomogeneous clouds, differences between REDvsNIR and the flux method can be as large as 50%. In addition, REDvsNIR agreed to better than 15% with the microwave method for both overcast and broken clouds. The second method, dubbed COUPLED, retrieves τ by combining zenith radiances with fluxes. While extra information from fluxes was expected to improve retrievals, this is not always the case. In general, however, the COUPLED and REDvsNIR methods retrieve τ to within 15% of each other.

Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

Laboratory measurements of the water vapor continuum in the 1200–8000 cm−1 region between 293 K and 351 K

Laboratory Fourier transform spectroscopy of pure water vapor and water vapor mixed with air has been conducted between 1200 and 8000 cm−1 and at temperatures between 293 and 351 K with the purpose of detecting and characterizing the water vapor continuum. The spectral features of the continuum within the major water absorption bands are presented and compared where possible to those from previous experimental studies and to the commonly used MT_CKD and CKD models. It was observed that in the main, both models adequately capture the general spectral form of the continuum; however, there were a number of exceptions. Overall, there is no evidence to indicate that MT_CKD is an improvement upon the older CKD model in these spectral regions. There was generally good agreement between our results and those of other experimental investigators. The general mathematical forms of the self-continuum temperature dependence, given by both Roberts et al. (1976) and CKD/MT_CKD, fit well to the experimental continuum in these spectral regions. However, the range of temperatures over which we made measurements is not sufficient to discriminate between these two forms or to exclude the possibility of other forms of temperature dependence being more appropriate. At the same time, the actual parameters currently used in CKD/MT_CKD to describe the temperature dependence in many spectral regions cannot reproduce the observed strong spectral variation in the temperature dependence. It has not been possible to make definitive conclusions about the magnitude of the continuum absorption in the far wings of the absorption bands investigated here.

Time-resolved gas-phase kinetic study of the germylene addition reaction, GeH2 + C2D2

Time-resolved studies of germylene, GeH2, generated by laser. ash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate coefficients for its bimolecular reaction with C2D2. The reaction was studied in the gas phase, mainly at a total pressure of 1.3 kPa (in SF6 bath gas) at five temperatures in the range 298-558 K. Pressure variation measurements over the range 0.13-13 kPa ( SF6) at 298, 397 and 558 K revealed a small pressure dependence but only at 558 K. After correction for this, the second-order rate coefficients gave the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1)) = (-10.96 +/- 0.05) + ( 6.16 +/- 0.37 kJ mol(-1))/RT ln 10 Comparison with the reaction of GeH2 + C2H2 (studied earlier) showed a similar behaviour with almost identical rate coefficients. The lack of a significant isotope effect is consistent with a rate-determining addition process and is explained by irreversible decomposition of the reaction intermediate to give Ge(P-3) + C2H4. This result contrasts with that for GeH2 + C2H4/C2D4 and those for the analogous silylene reactions. The underlying reasons for this are discussed.