X-ray Fluorescence Analysis of Feldspars and Silicate Glass: Effects of Melting Time on Fused Bead Consistency and Volatilisation

Reproducible preparation of lithium tetraborate fused beads for XRF analysis of glass and mineral samples is of paramount importance for analytical repeatability. However, as with all glass melting processes, losses due to volatilisation must be taken into account and their effects are not negligible. Here the effects of fused bead melting time have been studied for four Certified Reference Materials (CRM’s: three feldspars, one silicate glass), in terms of their effects on analytical variability and volatilisation losses arising from fused bead preparation. At melting temperatures of 1065 °C, and for feldspar samples, fused bead melting times shorter than approximately 25 min generally gave rise to a greater deviation of the XRF-analysed composition from the certified composition. This variation might be due to incomplete fusion and/or fused bead inhomogeneity but further research is needed. In contrast, the shortest fused bead melting time for the silicate glass CRM gave an XRF-analysed composition closer to the certified values than longer melting times. This may suggest a faster rate of glass-in-glass dissolution and homogenization during fused bead preparation. For all samples, longer melting times gave rise to greater volatilisation losses (including sulphates and halides) during fusion. This was demonstrated by a linear relationship between SO3 mass loss and time1/2, as predicted by a simple diffusion-based model. Iodine volatilisation displays a more complex relationship, suggestive of diffusion plus additional mechanisms. This conclusion may have implications for vitrification of iodine-bearing radioactive wastes. Our research demonstrates that the nature of the sample material impacts on the most appropriate fusion times. For feldspars no less than ~25 min and no more than ~60 min of fusion at 1065 °C, using Li2B4O7 as the fusion medium and in the context of feldspar samples and the automatic fusion equipment used here, strikes an acceptable (albeit non-ideal) balance between the competing factors of fused bead quality, analytical consistency and mitigating volatilisation losses. Conversely, for the silicate glass sample, shorter fusion times of less than ~30 min under the same conditions provided more accurate analyses whilst limiting volatile losses

X-Ray fluorescence analysis of feldspars and silicate glass: effects of melting time on fused bead consistency and volatilisation

Reproducible preparation of lithium tetraborate fused beads for XRF analysis of glass and mineral samples is of paramount importance for analytical repeatability. However, as with all glass melting processes, losses due to volatilization must be taken into account and their effects are not negligible. Here the effects of fused bead melting time have been studied for four Certified Reference Materials (CRM’s-three feldspars, one silicate glass), in terms of their effects on analytical variability and volatilization losses arising from fused bead preparation. At melting temperatures of 1065 °C, and for feldspar samples, fused bead melting times shorter than approximately 25 minutes generally gave rise to greater deviation of XRF-analyzed composition from certified composition. This variation might be due to incomplete fusion and / or fused bead inhomogeneity but further research is needed. In contrast, the shortest fused bead melting time for the silicate glass CRM gave an XRF-analyzed composition closer to the certified values than longer melting times. This may suggest a faster rate of glass-in-glass dissolution and homogenization during fused bead preparation. For all samples, longer melting times gave rise to greater volatilization losses (including sulphates and halides) during fusion. This was demonstrated by a linear relationship between SO3 mass loss and time1/2, as predicted by a simple diffusion-based model. Iodine volatilization displays a more complex relationship, suggestive of diffusion plus additional mechanisms. This conclusion may have implications for vitrification of iodine-bearing radioactive wastes. Our research demonstrates that the nature of the sample material impacts on the most appropriate fusion times. For feldspars no less than ~25 min and no more than ~60 min of fusion at 1065 °C, using Li2B4O7 as the fusion medium and in the context of feldspar samples and the automatic fusion equipment used here, strikes an acceptable (albeit non-ideal) balance between the competing factors of fused bead quality, analytical consistency and mitigating volatilization losses. Conversely, for the silicate glass sample, shorter fusion times of less than ~30 minutes under the same conditions provided more accurate analyses whilst limiting volatile losses

National and regional net nitrogen balances in Finland in 1990-2005

Nitrogen (N) balance has been identified as a principal agri-environmental indicator. In addition to national N balances, calculation of N balances for different agricultural regions is also recommended. In this study, national and regional net N balances for Finland were calculated. The net N balance is the result of deducting the NH3-N losses from manure and fertilisers from the gross N balance. The N balance calculation was based on data for Finnish Rural Centres and calculated per cultivated hectare. The main data inputs for the calculations were agricultural and environmental statistics, coefficients of manure excretion and crop N concentrations. Finnish national net N balance decreased from 90 kg ha–1 in 1990 to 50 kg ha–1 in 2005. The decrease in regional N balances was of the same magnitude. The main reason for the lower N balances was reduced use of mineral N fertilisers. Variation in the N balances was due to yield levels varying according to growing season conditions. The Rural Centres with intensive animal production tended to generate the highest N balances

Nitrification-denitrification in WSP: a mechanism for permanent nitrogen removal in maturation ponds

A pilot-scale primary maturation pond was spiked with 15N-labelled ammonia (15NH4Cl) and 15N labelled nitrite (Na15NO2), in order to improve current understanding of the dynamics of inorganic nitrogen transformations and removal in WSP systems. Stable isotope analysis of δ15N showed that nitrification could be considered as an intermediate step in WSP, which is masked by simultaneous denitrification, under conditions of low algal activity. Molecular microbiology analysis showed that denitrification can be considered a feasible mechanism for permanent nitrogen removal in WSP, which may be supported either by ammonia-oxidising bacteria (AOB) or by methanotrophs, in addition to nitrite-oxidising bacteria (NOB). However, the relative supremacy of the denitrification process over other nitrogen removal mechanisms (e.g., biological uptake) depends upon phytoplanktonic activity

A screening method for ranking chemicals by their fate and behaviour in the environment and potential toxic effects in humans following non-occupational exposure

A large number of chemicals are released intentionally or unintentionally into the environment each year. These include thousands of substances that are currently listed worldwide and several hundred new substances added annually (Mücke et al., 1986). When these compounds are used, they can reach microorganisms, plants, animals and man either in their original state or in the form of reaction and degradation products via air, water, soil or foodstuffs. Hence environmental chemicals can occur in practically all environmental compartments and ecosystems. It is not feasible to conduct assessments of human exposure and possible associated health effects for all chemicals. Even if the necessary resources were available, reliable data for a quantitative evaluation are likely to be absent in most cases. This has led to the development of schemes for prioritising compounds likely to be of environmental significance. Such schemes can be used to direct future research efforts towards the prioritised compounds. This study was commissioned by the Department of Health (DH) as part of a broader research activity that aims to identify key priority chemicals of concern to human health at routine levels of environmental exposure. The main pathways of human exposure are shown in Figure 1.1. A review of the principal prioritisation schemes used by different organisations to assess the significance of chemical release into the environment has been conducted by the MRC Institute for Environment and Health (IEH, 2003). This review showed that the approaches used by different organisations vary widely, depending on the initial reasons for which the schemes were developed. The basic information presented in the review was used to develop a simple screening method for ranking chemicals. The model used in this prioritisation scheme is outlined in Figure 1.2. The main purpose in developing the prioritisation scheme for DH was to develop a dedicated priority setting method capable of identifying chemicals in air, water, soil and foodstuffs that might pose a significant risk to human health following low level environmental exposure. The methodology was developed in order to identify compounds that required further assessment and those that had data gaps. More detailed risk assessments were conducted at a later stage on those compounds prioritised as being of high importancea. The screening methodology was developed for ‘existing chemicals’ as these are of greatest concern because data on their toxicity and/or fate and behaviour are often unknownb. The production of a priority list was designed to highlight compounds that required further regulatory measures to reduce exposure of the general population and for which an in-depth risk characterisation would be necessary to assist in the evaluation and implementation of activities for reducing environmental risks. This might include an assessment of the costs of such risks to human health and the costs of reduction measures. As the scheme also aimed to identify data gaps that might warrant further investigation, the application of default categories for chemicals with no data was also considered. The overall aim was to develop a screening methodology that is quick, clear and simple to use and that can easily be revised to take into account new information on compounds as and when it becomes available. a Benzene (IEH Report on Benzene in the Environment, R12); 4,6-dichlorocresol, hexachloro-1,3-butadiene, tetrachlorobenzene, 2,4,6-trichlorophenol (reports to DH; available from MRC Institute for Environment and Health b ‘Existing Substances’ are those that were placed in the European Union (EU) market before 1981. Prior to 1981 regulatory requirements were related to products intended for certain uses (e.g. veterinary medicines) and did not require assessment of the hazardous properties of any substance before they were released into the market. For substances placed on the market after 1981 (classified as ‘New Substances’) there is a legal requirement to conduct such assessments. Regulatory agencies require the collection of extensive documentation for safety before a chemical, for example, can be used in foods or commercial products. IEH Web Report W14, posted March 2004 at http://www.le.ac.uk/ieh/ 4 This report describes how physicochemical properties and toxicological data were incorporated into a screening model to assess the potential fate and transfer of chemicals between different environmental compartments and to predict the potential human exposure to toxic chemicals through the inhalation of contaminated air and the ingestion of water and food. It must be stressed, however, that the method devised is a simple screening process and that a more detailed assessment is necessary to determine the potential transfer through the foodchain of a chemical and the full extent of any adverse health effects. Sections 2 and 4 present the physicochemical properties, toxicological data and algorithms used to screen the compounds. Section 3 summarises the groups of chemicals that were included in the screening process. The results of the prioritisation scheme and comments on their limitations and constraints are presented in Section 5

Impact of aeration on the removal of organic matter and nitrogen compounds in constructed wetlands treating the liquid fraction of piggery manure

The increasing demand for sustainable, robust and cost-efficient wastewater treatment techniques strengthen the implementation of constructed wetlands (CWs) in the agricultural sector. In countries like Belgium (Flanders), the compliance of strict water quality standards and surface area requirements have hindered considerably their application. New wetland designs such as aerated CWs, could help to overcome these challenges. This study evaluated the capacity of artificially aerated mesocosm systems to decrease chemical oxygen demand (COD) concentrations below the 125 mgO(2)/L limit imposed on installations treating animal manure. The treatment of this high-strength wastewater has been slightly studied via aerated CWs. A three-stage experiment investigated the effect of constant, intermittent and non-aeration regimes on: ammonium volatilisation, the evolution of organic and nitrogen compounds concentrations, and denitrification. The results were assessed through a mixed modelling procedure using SAS 9.4 software. A COD removal between 65% and 58% in constantly and intermittent aerated systems, versus 27% COD removal in the non-aerated system indicated the effectiveness of aeration. However, a dissimilarity was encountered in the removal of nitrogen compounds, resulting in an 82% decrease of nitrate concentrations in the non-aerated system, versus 0.5% and 11% in the aerated ones. Based on the results, this experimental set-up adjusted to field operational conditions can prove that aerated CWs can treat the liquid fraction of piggery manure

Tracking nitrogen losses in a greenhouse crop rotation experiment in North China using the EU-Rotate_N simulation model

Vegetable production in China is associated with high inputs of nitrogen, posing a risk of losses to the environment. Organic matter mineralisation is a considerable source of nitrogen (N) which is hard to quantify. In a two-year greenhouse cucumber experiment with different N treatments in North China, non-observed pathways of the N cycle were estimated using the EU-Rotate_N simulation model. EU-Rotate_N was calibrated against crop dry matter and soil moisture data to predict crop N uptake, soil mineral N contents, N mineralisation and N loss. Crop N uptake (Modelling Efficiencies (ME) between 0.80 and 0.92) and soil mineral N contents in different soil layers (ME between 0.24 and 0.74) were satisfactorily simulated by the model for all N treatments except for the traditional N management. The model predicted high N mineralisation rates and N leaching losses, suggesting that previously published estimates of N leaching for these production systems strongly underestimated the mineralisation of N from organic matter

Characterization of iodine particles with Volatilization-Humidification Tandem Differential Mobility Analyser (VH-TDMA), Raman and SEM techniques

Particles formed upon photo-oxidation of CH2I2 and particles of I2O5 and HIO3 have been studied using a Volatilisation and Humidification Tandem Differential Mobility Analyser (VH-TDMA) system. Volatilization and hygroscopic behaviour have been investigated as function of temperature (from 25 to 400 degrees Celsius), humidity (RH from 80 to 98%), initial aerosol sizes (from 27 to 100 nm mobility diameter) and in nitrogen or air as the sheath gasses. The volatility behaviour of particles formed upon photo-oxidation of CH2I2 is more similar to that of HIO3 particles in a filtered sheath air than in nitrogen, with the particle shrinkage occurring at 190 degrees Celsius and accompanied by hygroscopic growth. Despite its high solubility, HIO3 was found not to be hygroscopic at room temperature with no significant growth displayed until the thermodenuder temperature reached 200 degrees Celsius or above when the particles have transformed into I2O5. Diiodopentaoxide (I2O5) particles exhibit relatively low hygroscopic growth factors of 1.2-2 in the humidity range investigated. Scanning Electron Microscopy (SEM) of particles formed upon photo-oxidation of CH2I2 shows that their primary elemental components were iodine and oxygen in a stoichiometric ratio of approximately 1:2 with 10% error. Both Raman spectra and SEM show poor crystallinity for all the aerosols produced