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.

Multi-season eddy covariance observations of energy, water and carbon fluxes over a suburban area in Swindon, UK

Eddy covariance measurements of the turbulent sensible heat, latent heat and carbon dioxide fluxes for 12 months (2011–2012) are reported for the first time for a suburban area in the UK. The results from Swindon are comparable to suburban studies of similar surface cover elsewhere but reveal large seasonal variability. Energy partitioning favours turbulent sensible heat during summer (midday Bowen ratio 1.4–1.6) and latent heat in winter (0.05–0.7). A significant proportion of energy is stored (and released) by the urban fabric and the estimated anthropogenic heat flux is small but non-negligible (0.5–0.9 MJ m−2 day−1). The sensible heat flux is negative at night and for much of winter daytimes, reflecting the suburban nature of the site (44% vegetation) and relatively low built fraction (16%). Latent heat fluxes appear to be water limited during a dry spring in both 2011 and 2012, when the response of the surface to moisture availability can be seen on a daily timescale. Energy and other factors are more relevant controls at other times; at night the wind speed is important. On average, surface conductance follows a smooth, asymmetrical diurnal course peaking at around 6–9 mm s−1, but values are larger and highly variable in wet conditions. The combination of natural (vegetative) and anthropogenic (emission) processes is most evident in the temporal variation of the carbon flux: significant photosynthetic uptake is seen during summer, whilst traffic and building emissions explain peak release in winter (9.5 g C m−2 day−1). The area is a net source of CO2 annually. Analysis by wind direction highlights the role of urban vegetation in promoting evapotranspiration and offsetting CO2 emissions, especially when contrasted against peak traffic emissions from sectors with more roads. Given the extent of suburban land use, these results have important implications for understanding urban energy, water and carbon dynamics.

SPARC Data Initiative: Comparison of water vapor climatologies from international satellite limb sounders

Within the SPARC Data Initiative, the first comprehensive assessment of the quality of 13 water vapor products from 11 limb-viewing satellite instruments (LIMS, SAGE II, UARS-MLS, HALOE, POAM III, SMR, SAGE III, MIPAS, SCIAMACHY, ACE-FTS, and Aura-MLS) obtained within the time period 1978-2010 has been performed. Each instrument's water vapor profile measurements were compiled into monthly zonal mean time series on a common latitude-pressure grid. These time series serve as basis for the "climatological" validation approach used within the project. The evaluations include comparisons of monthly or annual zonal mean cross sections and seasonal cycles in the tropical and extratropical upper troposphere and lower stratosphere averaged over one or more years, comparisons of interannual variability, and a study of the time evolution of physical features in water vapor such as the tropical tape recorder and polar vortex dehydration. Our knowledge of the atmospheric mean state in water vapor is best in the lower and middle stratosphere of the tropics and midlatitudes, with a relative uncertainty of. 2-6% (as quantified by the standard deviation of the instruments' multiannual means). The uncertainty increases toward the polar regions (+/- 10-15%), the mesosphere (+/- 15%), and the upper troposphere/lower stratosphere below 100 hPa (+/- 30-50%), where sampling issues add uncertainty due to large gradients and high natural variability in water vapor. The minimum found in multiannual (1998-2008) mean water vapor in the tropical lower stratosphere is 3.5 ppmv (+/- 14%), with slightly larger uncertainties for monthly mean values. The frequently used HALOE water vapor data set shows consistently lower values than most other data sets throughout the atmosphere, with increasing deviations from the multi-instrument mean below 100 hPa in both the tropics and extratropics. The knowledge gained from these comparisons and regarding the quality of the individual data sets in different regions of the atmosphere will help to improve model-measurement comparisons (e.g., for diagnostics such as the tropical tape recorder or seasonal cycles), data merging activities, and studies of climate variability.

Climate change and water in the UK: past changes and future prospects

Climate change is expected to modify rainfall, temperature and catchment hydrological responses across the world, and adapting to these water-related changes is a pressing challenge. This paper reviews the impact of anthropogenic climate change on water in the UK and looks at projections of future change. The natural variability of the UK climate makes change hard to detect; only historical increases in air temperature can be attributed to anthropogenic climate forcing, but over the last 50 years more winter rainfall has been falling in intense events. Future changes in rainfall and evapotranspiration could lead to changed flow regimes and impacts on water quality, aquatic ecosystems and water availability. Summer flows may decrease on average, but floods may become larger and more frequent. River and lake water quality may decline as a result of higher water temperatures, lower river flows and increased algal blooms in summer, and because of higher flows in the winter. In communicating this important work, researchers should pay particular attention to explaining confidence and uncertainty clearly. Much of the relevant research is either global or highly localized: decision-makers would benefit from more studies that address water and climate change at a spatial and temporal scale appropriate for the decisions they make

High-frequency water quality monitoring in an urban catchment: hydrochemical dynamics, primary production and implications for the Water Framework Directive

This paper describes the hydrochemistry of a lowland, urbanised river-system, The Cut in England, using in situ sub-daily sampling. The Cut receives effluent discharges from four major sewage treatment works serving around 190,000 people. These discharges consist largely of treated water, originally abstracted from the River Thames and returned via the water supply network, substantially increasing the natural flow. The hourly water quality data were supplemented by weekly manual sampling with laboratory analysis to check the hourly data and measure further determinands. Mean phosphorus and nitrate concentrations were very high, breaching standards set by EU legislation. Though 56% of the catchment area is agricultural, the hydrochemical dynamics were significantly impacted by effluent discharges which accounted for approximately 50% of the annual P catchment input loads and, on average, 59% of river flow at the monitoring point. Diurnal dissolved oxygen data demonstrated high in-stream productivity. From a comparison of high frequency and conventional monitoring data, it is inferred that much of the primary production was dominated by benthic algae, largely diatoms. Despite the high productivity and nutrient concentrations, the river water did not become anoxic and major phytoplankton blooms were not observed. The strong diurnal and annual variation observed showed that assessments of water quality made under the Water Framework Directive (WFD) are sensitive to the time and season of sampling. It is recommended that specific sampling time windows be specified for each determinand, and that WFD targets should be applied in combination to help identify periods of greatest ecological risk. This article is protected by copyright. All rights reserved.

Improving productivity and water use efficiency: a case study of farms in England

The idea of Sustainable Intensification comes as a response to the challenge of avoiding resources such as land, water and energy being overexploited while increasing food production for an increasing demand from a growing global population. Sustainable Intensification means that farmers need to simultaneously increase yields and sustainably use limited natural resources, such as water. Within the agricultural sector water has a number of uses including irrigation, spraying, drinking for livestock and washing (vegetables, livestock buildings). In order to achieve Sustainable Intensification measures are needed that enable policy makers and managers to inform them about the relative performance of farms as well as of possible ways to improve such performance. We provide a benchmarking tool to assess water use (relative) efficiency at a farm level, suggest pathways to improve farm level productivity by identifying best practices for reducing excessive use of water for irrigation. Data Envelopment Analysis techniques including analysis of returns to scale were used to evaluate any excess in agricultural water use of 66 Horticulture Farms based on different River Basin Catchments across England. We found that farms in the sample can reduce on average water requirements by 35% to achieve the same output (Gross Margin) when compared to their peers on the frontier. In addition, 47% of the farms operate under increasing returns to scale, indicating that farms will need to develop economies of scale to achieve input cost savings. Regarding the adoption of specific water use efficiency management practices, we found that the use of a decision support tool, recycling water and the installation of trickle/drip/spray lines irrigation system has a positive impact on water use efficiency at a farm level whereas the use of other irrigation systems such as the overhead irrigation system was found to have a negative effect on water use efficiency.

Water, irrigation and plant diseases

Irrigation is a major husbandry tool, vital for world food production and security. The purpose of this review is twofold:- firstly drawing attention to the beneficial and deleterious aspects of irrigation resulting from interactions with the microbial world; secondly, forming a basis for encouraging further research and development. Irrigation is for example, a valuable component in the control of some soil borne pathogens such as Streptomyces scabies, the cause of potato common scab and Fusarium cubense, a cause of banana wilt. By contrast, applying irrigation encourages some foliar pathogens and factors such as splash dispersal of propagules and the retention of leaf wetness are important elements in the successful establishment of disease foci. Irrigation applied at low levels in the canopy directly towards the stem bases and root zones of plants also provides means encouraging disease development. Irrigation also offers means for the direct spread of microbes such as water borne moulds, Oomycetes, and plasmodial pathogens coming from populations present in the water supply. The presence of plant disease causing microbes in sources of irrigation has been associated with outbreaks of diseases such as clubroot (Plasmodiophora brassicae). Irrigation can be utilised as a means for applying agrochemicals, fungigation. The developing technologies of water restriction and root zone drying also have an impact on the success of disease causing organisms. This is an emerging technology and its interactions with benign and pathogenic microbes require consideration.

Separation of natural colorants from the fermented broth of filamentous fungi using colloidal gas aphrons

There is a worldwide interest in the development of processes for producing colorants from natural sources. Microorganisms provide an alternative source of natural colorants produced by cultivation technology and extracted from the fermented broth. The aim of the present work was to study the recovery of red colorants from the fermented broth of Talaromyces amestolkiae using the technique of colloidal gas aphrons (CGA) comprising surfactant-stabilized microbubbles. Preliminary experiments were performed to evaluate the red colorants’ solubility in different organic solvents, octanol/water partitioning, and their stability in surfactant solutions, namely hexadecyl trimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylenesorbitan monolaurate (Tween 20), which are cationic, anionic and nonionic surfactants, respectively. The first recovery experiments were carried out using CGA generated by these surfactants at different volumetric ratios (VR, 3–18). Subsequently, two different approaches to generate CGA were investigated at VR values of 6 and 12: the first involved the use of CTAB at pH 6.9–10.0, and the second involved the use of Tween 20 using red colorants partially dissolved in ethanol and Tween 20. The characterization results showed that red colorants have a hydrophilic nature. The highest recoveries were obtained with Tween 20 (78%) and CTAB (70%). These results demonstrated that the recovery of the colorants was driven by both electrostatic and hydrophobic interactions. The VR was found to be an important operating parameter and at VR 12 with CTAB (at pH 9) maximum recovery, partitioning coefficient (K = 5.39) and selectivity in relation to protein and sugar (SP = 3.75 and SS = 7.20 respectively) were achieved. Furthermore, with Tween 20, the separation was driven mainly by hydrophobic interactions. Overall CGA show promise for the recovery of red colorants from a fermented broth. Although better results were obtained with CTAB than with Tween 20 the latter may be more suitable for some application due to its lower toxicity.

Assessment of production efficiency, physicochemical properties and storage stability of spray-dried chlorophyllide, a natural food colourant, using gum Arabic, maltodextrin and soy protein isolate-based carrier systems

P>The aim of this research was to study spray drying as potential action to protect chlorophyllide from environmental conditions for shelf-life extension and characterisation of the powders. Six formulations were prepared with 7.5 and 10 g of carrier agents [gum Arabic (GA), maltodextrin (MA) and soybean protein isolate (SPI)]/100 mL of chlorophyllide solutions. The powders were evaluated for morphological characteristics (SEM), particle size, water activity, moisture, density, hygroscopicity, cold water solubility, sorption isotherms, colour and stability, during 90 days. All the powders were highly soluble, with solubility values around 97%. A significant lower hygroscopicity was observed for GA powders, whilst the lower X(m) values obtained by GAB equation fitting of the sorption isotherms was observed for the 7.5 g MA/100 mL samples. All formulations, but the 1 (7.5 g SPI/100 mL of chlorophyllide), provided excellent stability to the chlorophyllide during 90 days of storage even at room temperature.

Effects of natural weathering on microstructure and mineral composition of cementitious roofing tiles reinforced with fique fibre

The objective of the present work was to evaluate the effects of 14 years of weathering exposition on the microstructure and mineral composition of cementitious roofing tiles, still in service, reinforced with fique fibres (Furcrae gender). The results show that tiles under weathering exposition presented higher water absorption and apparent void volume than tiles under laboratory exposition. The continuous hydration of cement and natural carbonation filled the smaller pores but contrarily the large pores remained in the porous fibre to matrix interface in the samples exposed to weathering. On the other hand, their microstructure presented lower air permeability than samples aged in the internal environment of the laboratory. Besides, in the weathering aged tiles takes place a more intensive hydration process as it was identified greater amount of hydrated phases than in the laboratory aged specimens. The present results contribute to understanding the consequences of tropical weathering on the fibre-cement degradation. (C) 2010 Elsevier Ltd. All rights reserved.

Natural antimicrobial ingredients incorporated in biodegradable films based on cassava starch

Biodegradable films based on cassava starch and with addition of natural antimicrobial ingredients were prepared using the casting technique. The tensile properties tensile strength (TS) [MPa] and percent elongation (E) at break [%] and the water vapor transmission (WVT) of the biodegradable films were evaluated and compared with the control (without antimicrobial ingredients). The evaluation of the Colony Forming Units per gram [CFU/g] of pan bread slices packed with the best biodegradable films, in terms of packaging performance, was also determined. The addition onto the matrix of only clove and cinnamon powders could reduce the films WVT when compared to the control, however TS and E were lower than the control and the effect of cinnamon was milder regarding this property. Since water activity of the pan bread slices packed with the biodegradable films increased considerably during the storage period, the antimicrobial effect could not be clearly determined. (C) 2010 Published by Elsevier Ltd.

The land-atmosphere water flux in the tropics

Tropical vegetation is a major source of global land surface evapotranspiration, and can thus play a major role in global hydrological cycles and global atmospheric circulation. Accurate prediction of tropical evapotranspiration is critical to our understanding of these processes under changing climate. We examined the controls on evapotranspiration in tropical vegetation at 21 pan-tropical eddy covariance sites, conducted a comprehensive and systematic evaluation of 13 evapotranspiration models at these sites, and assessed the ability to scale up model estimates of evapotranspiration for the test region of Amazonia. Net radiation was the strongest determinant of evapotranspiration (mean evaporative fraction was 0.72) and explained 87% of the variance in monthly evapotranspiration across the sites. Vapor pressure deficit was the strongest residual predictor (14%), followed by normalized difference vegetation index (9%), precipitation (6%) and wind speed (4%). The radiation-based evapotranspiration models performed best overall for three reasons: (1) the vegetation was largely decoupled from atmospheric turbulent transfer (calculated from X decoupling factor), especially at the wetter sites; (2) the resistance-based models were hindered by difficulty in consistently characterizing canopy (and stomatal) resistance in the highly diverse vegetation; (3) the temperature-based models inadequately captured the variability in tropical evapotranspiration. We evaluated the potential to predict regional evapotranspiration for one test region: Amazonia. We estimated an Amazonia-wide evapotranspiration of 1370 mm yr(-1), but this value is dependent on assumptions about energy balance closure for the tropical eddy covariance sites; a lower value (1096 mm yr(-1)) is considered in discussion on the use of flux data to validate and interpolate models.

Phase change and pyroelectricity in natural hemimorphite

The phase change of a natural hemimorphite sample from Minas Gerais (Brazil) was investigated by two X-ray diffraction (XRD) methods and by near-infrared reflectance spectroscopy. Applying successive thermal treatments, the crystal structure undergoes two orientation conversions. The first one occurs at about 550 degrees C, and it was revealed by the Laue method. Below 500 degrees C, the water molecules were partially expelled without changing the crystal structure. A fact that supports this statement is the sequential disappearance of the water bands at 1400 and 1900 nm by thermal treatment. The second conversion takes place below 939 degrees C. Moreover, at 972 degrees C a phase change to the willemite mineral (alpha-Zn(2)SiO(4)) has been observed. This last conversion was confirmed by the power XRD. In addition, natural hemimorphite displayed a high pyroelectricity, which is related both to the absence of inverse centre and to the presence of molecular water and hydroxyl groups in the crystal structure.

Very low optical absorptions and analyte concentrations in water measured by Optimized Thermal Lens Spectrometry

Thermal Lens Spectrometry has traditionally been carried out in the single-beam and the mode-mismatched dual-beam configurations. Recently, a much more sensitive dual-beam TL setup was developed, where the probe beam is expanded and collimated. This feature optimizes Thermal Lens (TL) signal and allows the use of thicker samples, further improving the sensitivity. In this paper, we have made comparisons between the conventional and optimized TL configurations, and presented applications such as measurements of very low absorptions and concentrations in water and Cr(III) aqueous solution in the UV-vis range. For pure water we found linear absorption coefficients as low as the Raman scattering one due to the stretching vibrational modes of OH group. The detection limit was estimated 1 x 10(-6) cm(-1) with a 180-mW excitation power using a 100-mm cell length. This sensitivity is very high, considering that water has a photothermal enhancement factor similar to 33 times smaller than CCl(4), for example. For Cr(III) species in aqueous solution, the limit of detection (LOD) was estimated in similar to 40 ng mL(-1) at 514 nm, or similar to 10ng mL(-1) at 405 nm, which is similar to 30 times smaller than the LOD achieved with conventional transmission techniques. The more recent TL configuration is very attractive to obtain absorption spectra, since the result does not depend critically on the beam parameters, unlike the other configurations. The main drawbacks of this optimized TL configuration are the longer acquisition time and the need for larger samples. (C) 2011 Published by Elsevier B.V.

Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.