The determination of total nitrogen and total phosphorus concentrations in freshwaters from land use, stock headage and population data: testing of a model for use in conservation and water quality management

1. Nutrient concentrations (particularly N and P) determine the extent to which water bodies are or may become eutrophic. Direct determination of nutrient content on a wide scale is labour intensive but the main sources of N and P are well known. This paper describes and tests an export coefficient model for prediction of total N and total P from: (i) land use, stock headage and human population; (ii) the export rates of N and P from these sources; and (iii) the river discharge. Such a model might be used to forecast the effects of changes in land use in the future and to hindcast past water quality to establish comparative or baseline states for the monitoring of change. 2. The model has been calibrated against observed data for 1988 and validated against sets of observed data for a sequence of earlier years in ten British catchments varying from uplands through rolling, fertile lowlands to the flat topography of East Anglia. 3. The model predicted total N and total P concentrations with high precision (95% of the variance in observed data explained). It has been used in two forms: the first on a specific catchment basis; the second for a larger natural region which contains the catchment with the assumption that all catchments within that region will be similar. Both models gave similar results with little loss of precision in the latter case. This implies that it will be possible to describe the overall pattern of nutrient export in the UK with only a fraction of the effort needed to carry out the calculations for each individual water body. 4. Comparison between land use, stock headage, population numbers and nutrient export for the ten catchments in the pre-war year of 1931, and for 1970 and 1988 show that there has been a substantial loss of rough grazing to fertilized temporary and permanent grasslands, an increase in the hectarage devoted to arable, consistent increases in the stocking of cattle and sheep and a marked movement of humans to these rural catchments. 5. All of these trends have increased the flows of nutrients with more than a doubling of both total N and total P loads during the period. On average in these rural catchments, stock wastes have been the greatest contributors to both N and P exports, with cultivation the next most important source of N and people of P. Ratios of N to P were high in 1931 and remain little changed so that, in these catchments, phosphorus continues to be the nutrient most likely to control algal crops in standing waters supplied by the rivers studied.

A procedure for the simultaneous determination of total nitrogen and total phosphorus in freshwater samples using persulphate microwave digestion

In the absence of a suitable method for routine analysis of large numbers of natural river water samples for organic nitrogen and phosphorus fractions, a new simultaneous digestion technique was developed, based on a standard persulphate digestion procedure. This allows rapid analysis of river, lake and groundwater samples from a range of environments for total nitrogen and phosphorus. The method was evaluated using a range of organic nitrogen and phosphorus structures tested at low, mid and high range concentrations from 2 to 50 mg l-1 nitrogen and 0.2 to 10 mg l-1 phosphorus. Mean recoveries for nitrogen ranged from 94.5% (2 mg I-1) to 92.7% (50 mg I-1) and for phosphorus were 98.2% (0.2 mg l-1) to 100.2% (10 mg l-1). The method is precise in its ability m reproduce results from replicate digestions, and robust in its ability to handle a variety of natural water samples in the pH range 5-8.

Determination of Holocene cave temperatures from Kr and Xe concentrations in stalagmite fluid inclusions

From the concentrations of dissolved atmospheric noble gases in water, a so-called “noble gas temperature” (NGT) can be determined that corresponds to the temperature of the water when it was last in contact with the atmosphere. Here we demonstrate that the NGT concept is applicable to water inclusions in cave stalagmites, and yields NGTs that are in good agreement with the ambient air temperatures in the caves. We analysed samples from two Holocene and one undated stalagmite. The three stalagmites originate from three caves located in different climatic regions having modern mean annual air temperatures of 27 °C, 12 °C and 8 °C, respectively. In about half of the samples analysed Kr and Xe concentrations originated entirely from the two well-defined noble gas components air-saturated water and atmospheric air, which allowed NGTs to be determined successfully from Kr and Xe concentrations. One stalagmite seems to be particularly suitable for NGT determination, as almost all of its samples yielded the modern cave temperature. Notably, this stalagmite contains a high proportion of primary water inclusions, which seem to preserve the temperature-dependent signature well in their Kr and Xe concentrations. In future work on stalagmites detailed microscopic inspection of the fluid inclusions prior to noble gas analysis is therefore likely to be crucial in increasing the number of successful NGT determinations.

Determination of tube theory parameters using a simple grid model as an example

Although the tube theory is successful in describing entangled polymers qualitatively, a more quantitative description requires precise and consistent definitions of its parameters. Here we investigate the simplest model of entangled polymers, namely a single Rouse chain in a cubic lattice of line obstacles, and illustrate the typical problems and uncertainties of the tube theory. In particular we show that in general one needs 3 entanglement related parameters, but only 2 combinations of them are relevant for the long-time dynamics. Conversely, the plateau modulus can not be determined from these two parameters and requires a more detailed model of entanglements with explicit entanglement forces, such as the slipsprings model. It is shown that for the grid model the Rouse time within the tube is larger than the Rouse time of the free chain, in contrast to what the standard tube theory assumes.

On the determination of atmospheric water vapor from GPS measurements

Surface-based GPS measurements of zenith path delay (ZPD) can be used to derive vertically integrated water vapor (IWV) of the atmosphere. ZPD data are collected in a global network presently consisting of 160 stations as part of the International GPS Service. In the present study, ZPD data from this network are converted into IWV using observed surface pressure and mean atmospheric water vapor column temperature obtained from the European Centre for Medium-Range Weather Forecasts' (ECMWF) operational analyses (OA). For the 4 months of January/July 2000/2001, the GPS-derived IWV values are compared to the IWV from the ECMWF OA, with a special focus on the monthly averaged difference (bias) and the standard deviation of daily differences. This comparison shows that the GPS-derived IWV values are well suited for the validation of OA of IWV. For most GPS stations, the IWV data agree quite well with the analyzed data indicating that they are both correct at these locations. Larger differences for individual days are interpreted as errors in the analyses. A dry bias in the winter is found over central United States, Canada, and central Siberia, suggesting a systematic analysis error. Larger differences were mainly found in mountain areas. These were related to representation problems and interpolation difficulties between model height and station height. In addition, the IWV comparison can be used to identify errors or problems in the observations of ZPD. This includes errors in the data itself, e.g., erroneous outlier in the measured time series, as well as systematic errors that affect all IWV values at a specific station. Such stations were excluded from the intercomparison. Finally, long-term requirements for a GPS-based water vapor monitoring system are discussed.

Determination of the gas diffusion coefficient of a peat grassland soil

Peatland habitats are important carbon stocks that also have the potential to be significant sources of greenhouse gases, particularly when subject to changes such as artificial drainage and application of fertilizer. Models aiming to estimate greenhouse gas release from peatlands require an accurate estimate of the diffusion coefficient of gas transport through soil (Ds). The availability of specific measurements for peatland soils is currently limited. This study measured Ds for a peat soil with an overlying clay horizon and compared values with those from widely available models. The Ds value of a sandy loam reference soil was measured for comparison. Using the Currie (1960) method, Ds was measured between an air-filled porosity (ϵ) range of 0 and 0.5 cm3 cm−3. Values of Ds for the peat cores ranged between 3.2 × 10−4 and 4.4 × 10−3 m2 hour−1, for loamy clay cores between 0 and 4.7 × 10−3 m2 hour−1 and for the sandy reference soil they were between 5.4 × 10−4 and 3.4 × 10−3 m2 hour−1. The agreement of measured and modelled values of relative diffusivity (Ds/D0, with D0 the diffusion coefficient through free air) varied with soil type; however, the Campbell (1985) model provided the best replication of measured values for all soils. This research therefore suggests that the use of the Campbell model in the absence of accurately measured Ds and porosity values for a study soil would be appropriate. Future research into methods to reduce shrinkage of peat during measurement and therefore allow measurement of Ds for a greater range of ϵ would be beneficial.

Determination of eddy-diffusivity in the lowermost stratosphere

We present a 2D-advection-diffusion model that simulates the main transport pathways influencing tracer distributions in the lowermost stratosphere (LMS). The model describes slow diabatic descent of aged stratospheric air, vertical (cross-isentropic) and horizontal (along isentropes) diffusion within the LMS and across the tropopause using equivalent latitude and potential temperature coordinates. Eddy diffusion coefficients parameterize the integral effect of dynamical processes leading to small scale turbulence and mixing. They were specified by matching model simulations to observed CO distributions. Interestingly, the model suggests mixing across isentropes to be more important than horizontal mixing across surfaces of constant equivalent latitude, shining new light on the interplay between various transport mechanisms in the LMS. The model achieves a good description of the small scale tracer features at the tropopause with squared correlation coefficients R2 = 0.72…0.94.

Determination of a lower bound on Earth’s climate sensitivity

Transient and equilibrium sensitivity of Earth's climate has been calculated using global temperature, forcing and heating rate data for the period 1970–2010. We have assumed increased long-wave radiative forcing in the period due to the increase of the long-lived greenhouse gases. By assuming the change in aerosol forcing in the period to be zero, we calculate what we consider to be lower bounds to these sensitivities, as the magnitude of the negative aerosol forcing is unlikely to have diminished in this period. The radiation imbalance necessary to calculate equilibrium sensitivity is estimated from the rate of ocean heat accumulation as 0.37±0.03W m^−2 (all uncertainty estimates are 1−σ). With these data, we obtain best estimates for transient climate sensitivity 0.39±0.07K (W m^−2)^−1 and equilibrium climate sensitivity 0.54±0.14K (W m^−2)^−1, equivalent to 1.5±0.3 and 2.0±0.5K (3.7W m^−2)^−1, respectively. The latter quantity is equal to the lower bound of the ‘likely’ range for this quantity given by the 2007 IPCC Assessment Report. The uncertainty attached to the lower-bound equilibrium sensitivity permits us to state, within the assumptions of this analysis, that the equilibrium sensitivity is greater than 0.31K (W m^−2)^−1, equivalent to 1.16K(3.7W m^−2)^−1, at the 95% confidence level.

Determination of orientations of aromatic groups in self-assembled peptide fibrils by polarised Raman spectroscopy

In this paper we describe a novel combination of Raman spectroscopy, isotope editing and X-ray scattering as a powerful approach to give detailed structural information on aromatic side chains in peptide fibrils. The orientation of the tyrosine residues in fibrils of the peptide YTIAALLSPYS with respect to the fibril axis has been determined from a combination of polarised Raman spectroscopy and X-ray diffraction measurements. The Raman intensity of selected tyrosine bands collected at different polarisation geometries is related to the values and orientation of the Raman tensor for those specific vibrations. Using published Raman tensor values we solved the relevant expressions for both of the two tyrosine residues present in this peptide. Ring deuteration in one of the two tyrosine side chains allowed for the calculation to be performed individually for both, by virtue of the isotopic shift that eliminates band overlapping. Sample disorder was taken into account by obtaining the distribution of orientations of the samples from X-ray diffraction experiments. The results provide previously unavailable details about the molecular conformation of this peptide, and demonstrate the value of this approach for the study of amyloid fibrils.

Potential of the slow component of quartz OSL for age determination of sedimentary samples

The slow component of quartz OSL exhibits a high thermal stability, and, in many of the samples studied, a high dose saturation level (several hundreds or, even thousands, of Grays). These properties suggest that the slow component has potential as a long-range dating tool. Initial attempts have been made to obtain equivalent doses for a number of sedimentary samples. Single- and multiple-aliquot techniques were modified for use with the slow component. The results indicate that there is a good potential for sediment dating, particularly for samples of significant age. Experiments concerning the optical resetting of the slow component suggest that, given its slow optical depletion rate, dating may be restricted to aeolian sediments.

Objective determination of feature resolution in two sea surface temperature analyses

Considerable effort is presently being devoted to producing high-resolution sea surface temperature (SST) analyses with a goal of spatial grid resolutions as low as 1 km. Because grid resolution is not the same as feature resolution, a method is needed to objectively determine the resolution capability and accuracy of SST analysis products. Ocean model SST fields are used in this study as simulated “true” SST data and subsampled based on actual infrared and microwave satellite data coverage. The subsampled data are used to simulate sampling errors due to missing data. Two different SST analyses are considered and run using both the full and the subsampled model SST fields, with and without additional noise. The results are compared as a function of spatial scales of variability using wavenumber auto- and cross-spectral analysis. The spectral variance at high wavenumbers (smallest wavelengths) is shown to be attenuated relative to the true SST because of smoothing that is inherent to both analysis procedures. Comparisons of the two analyses (both having grid sizes of roughly ) show important differences. One analysis tends to reproduce small-scale features more accurately when the high-resolution data coverage is good but produces more spurious small-scale noise when the high-resolution data coverage is poor. Analysis procedures can thus generate small-scale features with and without data, but the small-scale features in an SST analysis may be just noise when high-resolution data are sparse. Users must therefore be skeptical of high-resolution SST products, especially in regions where high-resolution (~5 km) infrared satellite data are limited because of cloud cover.