Preparation, certification and interlaboratory analysis of workplace air filters spiked with high-fired beryllium oxide

Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.     

A new multiscale approach for monitoring vegetation using remote sensing-based indicators in laboratory, field, and landscape

Remote sensing is an important tool for studying patterns in surface processes on different spatiotemporal scales. However, differences in the spatiospectral and temporal resolution of remote sensing data as well as sensor-specific surveying characteristics very often hinder comparative analyses and effective up- and downscaling analyses. This paper presents a new methodical framework for combining hyperspectral remote sensing data on different spatial and temporal scales. We demonstrate the potential of using the “One Sensor at Different Scales” (OSADIS) approach for the laboratory (plot), field (local), and landscape (regional) scales. By implementing the OSADIS approach, we are able (1) to develop suitable stress-controlled vegetation indices for selected variables such as the Leaf Area Index (LAI), chlorophyll, photosynthesis, water content, nutrient content, etc. over a whole vegetation period. Focused laboratory monitoring can help to document additive and counteractive factors and processes of the vegetation and to correctly interpret their spectral response; (2) to transfer the models obtained to the landscape level; (3) to record imaging hyperspectral information on different spatial scales, achieving a true comparison of the structure and process results; (4) to minimize existing errors from geometrical, spectral, and temporal effects due to sensor- and time-specific differences; and (5) to carry out a realistic top- and downscaling by determining scale-dependent correction factors and transfer functions. The first results of OSADIS experiments are provided by controlled whole vegetation experiments on barley under water stress on the plot scale to model LAI using the vegetation indices Normalized Difference Vegetation Index (NDVI) and green NDVI (GNDVI). The regression model ascertained from imaging hyperspectral AISA-EAGLE/HAWK (DUAL) data was used to model LAI. This was done by using the vegetation index GNDVI with an R ² of 0.83, which was transferred to airborne hyperspectral data on the local and regional scales. For this purpose, hyperspectral imagery was collected at three altitudes over a land cover gradient of 25 km within a timeframe of a few minutes, yielding a spatial resolution from 1 to 3 m. For all recorded spatial scales, both the LAI and the NDVI were determined. The spatial properties of LAI and NDVI of all recorded hyperspectral images were compared using semivariance metrics derived from the variogram. The first results show spatial differences in the heterogeneity of LAI and NDVI from 1 to 3 m with the recorded hyperspectral data. That means that differently recorded data on different scales might not sufficiently maintain the spatial properties of high spatial resolution hyperspectral images.     

A stress-strain model to evaluate the forest situation in Germany and the state of the art of damage research

The situation and the latest findings of forest damage research in Germany are discussed. A newly developed concept for this research is described. This concept allows to identify the drawbacks of the recent damage research concept but also the integration of results compiled up to now. The importance for including natural occurring stress factors such as climate, soil conditions or local situation of individual species is outlined.     

A gas-phase biosensor for environmental monitoring of formic acid: laboratory and field validation

In order to encourage more exposure measurements to be performed, a formic acid gas-phase biosensor has been developed for this purpose. In the present paper, an enzyme based biosensor has been validated with respect to analyte selectivity and on-site use. To ensure that the sampler developed measures the compound of interest the biosensor was exposed to three near structural homologues to formic acid, i.e. acetic acid, methanol and formaldehyde. These vapours were generated with and without formic acid and the only compound that was found to have an effect on the performance of the biosensor, albeit a small one, was acetic acid. The field test was performed in a factory using formic acid-containing glue for glulam products. In parallel to the measurements with the biosensor a well defined reference method was used for sampling and analysing formic acid. It was found that the biosensor worked satisfactorily in this environment when used in a stationary position. It was also shown that the biosensor could determine formic acid vapour concentrations down to 0.03 mg m(-3).     

Measurement of environmental pollutants using passive sampling devices--a commentary on the current state of the art

Passive sampling devices have been used since the 1970s to measure time-weighted average (TWA) or equilibrium concentrations of pollutants in various environmental matrices (e.g. air, soils and sediments and water). In recent years the popularity of using such samplers has increased and the technology in now well established for the measurement of atmospheric pollutants. This sector has a long experience of using passive samplers in the short- and long-term assessment of air quality in the local environment and on a global scale (e.g. within the United Nations Stockholm Convention on the trans-boundary movement of persistent organic pollutants (POPs) where large networks of samplers on a continental scale have been established). In comparison, the use of passive samplers for monitoring the aquatic environment has been slower to take off. There has, however, been a recent research drive to develop devices for measuring the wide range of pollutants that can be found in environmental waters (e.g. ground, surface, and marine). It is now being recognised that passive samplers can play a valuable role in monitoring water quality within a legislative framework such as the European Union's Water Framework Directive (WFD). The data from these devices can be used alongside the results obtained from conventional spot or bottle sampling to improve risk assessments and to inform decisions on undertaking potentially expensive remedial actions. Such monitoring techniques may have uses within the European Registration, Evaluation, Authorisation & restriction of CHemicals (REACH) Directive and the forthcoming European Marine Strategy Directive. It is expected that the aquatic monitoring sector will follow a transition similar to that which occurred in air monitoring where data obtained from passive samplers can use used within a legal framework. There has also been increased interest in extending the role of passive samplers to both the measurement of equilibrium concentrations and investigating the movement and release of the dissolved fraction of various pollutants in the pore water of sediments and soils.     

25 years of the UK EIA System: Strengths,weaknesses, opportunities and threats

This paper offers a review of the UK EIA system, providing insights into its evolution and reflecting on perceptions of effectiveness of the EIA system. The work adopts a similar approach used by Glasson in 1999, where he provided a review of the first 10 years of EIA in the UK, complimented by a SWOT analysis. In conducting the SWOT analysis, the authors make use of (1) a UK EIA survey which was conducted in 2011; (2) an interactive session organised at a 2013 workshop at the University of Liverpool on 25 years of the EU EIA Directive; and (3) a systematic literature review of publications since 1999. The results indicate that the internal factors (i.e. strengths and weaknesses) of the EIA system have not actually changed much in the last 15 years. Changes are more apparent for the external factors, especially with regards to opportunities. However, EIA may be suffering from a mid-life crisis at this point and a lot may be owing to perceptions towards EIA which may be influenced and inversely related to the length of experience in EIA. This opens up avenues for further research in the area.     

Determination of ethanolamine,ethylene glycol and triethylene glycol by ion chromatography for laboratory and field biodegradation studies

The determination of alkanolamines and glycols in groundwater and subsurface environments is essential for environmental assessment, remediation and monitoring for selected industrial sites. Monoethanolamine (MEA), ammonium, sodium, magnesium and calcium detection was performed using cation exchange chromatography (IC) with suppressed conductivity detection. Acetate, chloride, nitrite, nitrate, phosphate, sulfate and oxalate were monitored employing anion exchange chromatography with suppressed conductivity. Detection of ethylene glycol (MEG) and triethylene glycol (TEG) and ethanol was carried out using ion exclusion chromatography with pulsed amperometric detection. Effective determination of MEA, MEG and TEG in complex groundwater matrices without compound transformation offered improved monitoring capabilities. This study presents robust analytical tools for MEA, MEG and TEG determination in biodegradation studies. Using ion chromatography offered significant advantages for the analyses of groundwater samples and laboratory bioreactor monitoring.     

Deterioration of Jerusalem limestone from air pollutants; field observations and laboratory simulation

Samples of Jerusalem limestones were exposed to high levels of common air pollutants (SO₂, NO) in the presence and absence of hydrocarbon, water vapor and ultra-violet light. After exposure, the outer layers were shaved off and analyzed for sulfate and nitrate. The results revealed that even after one day of exposure significant concentrations of CaSO₄ and Ca(NO₃)₂ could be detected in the external 40 m layers. Sulfate formation was found to relate very strongly to relative humidity with nearly undetectable production at humidities below 10%. Nitrate formation was found to relate to UV light and to a limited extent to the presence of hydrocarbon but was unchanged at different humidities. Surface samples were taken from different sites of the old city wall and were also analyzed for the same substances. The data showed that the concentrations of especially CaSO₄, and to a limited extend Ca(NO₃)₂, measured at various points along the city walls were higher than the expected values extrapolated from laboratory simulations. The elevated pollution content may be explained in part due to the deposition of transported ions, especially sulfate, onto the stone surface. It was concluded that although air pollution may not cause any structural damage in the foreseeable future it definitely deteriorates the fine details of the ancient monument.     

Thermal monitoring and analysis of the large-scale field earth-dam breach process

Thermal imaging is a nondestructive testing method for monitoring internal material changes that are indicated by changes in an object’s surface temperature. In this study, field observation using thermographs was applied to monitor and analyze the breach process of large-scale earth dams. The earth dam test site was Landao Creek in Nantou County, Taiwan. Four field tests were performed to monitor and analyze a single earth dam and two successive earth dams. Ponding first occurred at the lowland of the riverbed upstream, and base seepage occurred at the base of the dam downstream; overtopping failure soon followed. Earth-dam failure mode is affected by the topographic characteristics of the riverbed; specifically, lowland areas are prone to ponding upstream, which causes piping and seepage downstream as well as subsequent breaches. Ponding and piping cause water seepage and soil wetting, which are reflected in lower surface temperatures recorded on thermographs. Thermographs can monitor changes in surface temperature to evaluate the potential failure modes of dams. Dam surfaces with large temperature variations may be potential failure areas. If confirmed, this fact may prove useful for failure-mode prediction. This paper proposes a monitoring index to reflect the temperature changes in a given period, and this study verified it empirically.     

Interlaboratory evaluation of an extraction and fluorescence method for the determination of trace beryllium in soils

Analytical methods for the determination of trace beryllium in soils are needed so that anthropogenic sources of this element can be distinguished from native (background) levels of beryllium. In this work, a collaborative interlaboratory evaluation of a new extraction and fluorescence-based procedure for determining beryllium in soil samples was carried out to fulfil method validation requirements for ASTM International voluntary consensus standard test methods. A Canadian reference material, CCRMP Till-1 soil, with a background beryllium concentration of 2.4 microg g(-1), was selected for study. This certified reference material (CRM) was spiked and homogenized with varying levels of beryllium oxide in order to give batches of material with beryllium concentrations of 4.36 +/- 0.69, 11.5 +/- 0.7, 124 +/- 7 and 246 +/- 16 microg g(-1) (+/- values are standard deviations). In the interlaboratory study (ILS), which was carried out in accordance with an applicable ASTM International standard practice (ASTM E691), samples of these spiked soils were subjected to extraction in dilute ammonium bifluoride at approximately 90 degrees C for 40 h. Fluorescence measurement of the extracted beryllium was carried out via detection using the high quantum yield fluorophore, hydroxybenzoquinoline sulfonate (HBQS). Interlaboratory precision estimates from six participating laboratories ranged from 0.048 to 0.103 (relative standard deviations) for the five different beryllium concentrations. Pooled bias estimates resulting from this ILS were between -0.049 and 0.177 for the various beryllium levels. These figures of merit support promulgation of the analytical procedure as an ASTM International standard test method.     

Current strategies in nitrite detection and their application to field analysis

The various analytical protocols that have been developed to aid the measurement of nitrite within environmental samples have been critically appraised and their applicability to field measurement assessed. The present communication presents a perspective on current techniques and technologies encompassing spectroscopic, electrochemical and chromatographic methodologies and highlights those that are liable to emerge in the near future. Commercial devices have been included and where appropriate the advantages and limitations posed by their operation within field contexts have been described.     

Application of portable gas chromatography-photo ionization detector combined with headspace sampling for field analysis of benzene, toluene, ethylbenzene, and xylene in soils

A method based on headspace (HS) sampling coupling with portable gas chromatography (GC) with photo ionization detector (PID) was developed for rapid determination of benzene, toluene, ethylbenzene, and xylenes (BTEX) in soils. Optimal conditions for HS gas sampling procedure were determined, and the influence of soil organic matter on the recovery of BTEX from soil was investigated using five representative Chinese soils. The results showed that the HS-portable-GC-PID method could be effectively operated at ambient temperature, and the addition of 15 ml of saturated NaCl solution in a 40-ml sampling vial and 60 s of shaking time for sample solution were optimum for the HS gas sampling procedure. The recoveries of each BTEX in soils ranged from 87.2 to 105.1 %, with relative standard deviations varying from 5.3 to 7.8 %. Good linearity was obtained for all BTEX compounds, and the detection limits were in the 0.1 to 0.8 μg kg^?1 range. Soil organic matter was identified as one of the principal elements that affect the HS gas sampling of BTEX in soils. The HS-portable-GC-PID method was successfully applied for field determination of benzene and toluene in soils of a former chemical plant in Jilin City, northeast China. Considering its satisfactory repeatability and reproducibility and particular suitability to be operated in ambient environment, HS sampling coupling with portable GC-PID is, therefore, recommended to be a suitable screening tool for rapid on-site determination of BTEX in soils.     

A review of citizen science and community-based environmental monitoring: issues and opportunities

Worldwide, decision-makers and nongovernment organizations are increasing their use of citizen volunteers to enhance their ability to monitor and manage natural resources, track species at risk, and conserve protected areas. We reviewed the last 10 years of relevant citizen science literature for areas of consensus, divergence, and knowledge gaps. Different community-based monitoring (CBM) activities and governance structures were examined and contrasted. Literature was examined for evidence of common benefits, challenges, and recommendations for successful citizen science. Two major gaps were identified: (1) a need to compare and contrast the success (and the situations that induce success) of CBM programs which present sound evidence of citizen scientists influencing positive environmental changes in the local ecosystems they monitor and (2) more case studies showing use of CBM data by decision-makers or the barriers to linkages and how these might be overcome. If new research focuses on these gaps, and on the differences of opinions that exist, we will have a much better understanding of the social, economic, and ecological benefits of citizen science.     

A review of workplace aerosol sampling procedures and their relevance to the assessment of beryllium exposures

Standardized conventions governing the fractions of airborne particles that can penetrate the human head airways, the thoracic airways and the alveolar spaces have been internationally (although not universally) adopted. Several agencies involved in setting limit values for occupational exposure concentrations have taken these conventions into account when considering the appropriate standard for specific chemicals, in order to ensure the standards are biologically relevant. A convention is selected based on the characteristic health effects, and forms the basis of measurement against the limiting concentration value. In order to assess exposure for comparison to this metric or any other purposes, it is necessary to choose a sampler whose performance matches the convention, and protocols have been developed and used to test sampler performance. Several aerosol sampling devices are available, nominally at least, for each of the conventions. Some considerations important to the sampling of airborne particles containing beryllium with regard to the sampling conventions, the test protocols and sampler performance are discussed.