Assessing workplace chemical exposures: the role of exposure monitoring

Occupational exposure is the condition of being subjected through employment to a chemical, physical, or biological agent, or to a specific process, practice, behavior, or organization of work. Exposure to a chemical agent is typically the contact of that agent with the outer boundary of a subject, such as the respiratory system, skin, or digestive system. In occupational hygiene we are most concerned with exposure through the respiratory system, although, increasingly we are concerned with the results of dermal exposures, including those exposures to the skin that can be transferred to the mouth and digestive system. This presentation will detail methods available for assessing personal exposures to chemicals through monitoring. The results from monitoring can then be compared to established guidelines and regulations, although this is not the only rationale for making measurements. These monitoring methods are currently used around the world to establish the benchmark hazard from which risk to the worker can be predicted. The presentation will describe the general techniques for assessing exposures to the respiratory system from chemical gases and vapors, chemical dusts, and exposures to the skin from bulk chemicals or chemical contamination of surfaces. For respiratory exposures, direct-reading instruments are available for spot measurements, and for monitoring short-term fluctuations in concentration. However, most standards and regulations are based on time-integrated (time-weighted average) exposures, requiring longer-term integrative methods. Therefore, the specific focus of this review will be the methods available for full work-shift sampling. For gases and vapors this will include taking whole-air samples in canisters or polymer bags, or concentration of chemicals by absorption in liquids or adsorption on solid sorbents, with subsequent chemical analysis. Chemical concentration can take place by pumping air through the sorbing media, or by allowing molecules to diffuse to the sorbent surface. Transfer of the collected chemicals to the analytical instrumentation can be accomplished using solvent displacement and injection, or through the application of heat to bring the collected molecules back into the vapor phase. For particles, the particle size is important as this determines the site of deposition in the lungs, and so time-integrated sampling on filters using various types of size-selective samplers is preferred. Finally, some techniques that have been used to assess the potential for chemical contamination of the skin are presented. Biomonitoring is another tool that can be used to assess exposure, and the results are more relevant to dosimetric considerations than exposure. Biomonitoring is a complex subject worthy of a separate review, and will be considered only briefly here.     

Two-phase jet releases,droplet dispersion and rainout I. Overview and model validation

Many accidents involve two-phase releases of hazardous chemicals into the atmosphere. This paper describes the results of the fourth phase of a Joint Industry Project (JIP) on liquid jets and two-phase droplet dispersion. The objective of Phase IV of the JIP was to generate experimental rainout data for non-flashing experiments, and to develop recommendations for the best methodology to predict rainout [total rainout mass and its spatial distribution (‘distributed’ rainout)].Phase IV of the JIP first included rainout experiments by the UK Health and Safety Laboratory (HSL) for sub-cooled releases of water and xylene with a range of orifice sizes and stagnation pressures. See the companion paper II for further details. Secondly model validation was carried out by DNV Software for these experiments using different correlations for the initial droplet size (Sauter Mean Diameter, SMD), i.e. the CCPS SMD correlation and the Phase III JIP SMD correlation. The validation includes flow rates, droplet size, distributed rainout and cloud temperature drop. Subsequently validation was considered for a wider range of experiments from the literature (sub-cooled and superheated releases) for both SMD and total rainout. Adopted rainout methods comprised both methods including explicit modelling of the droplets (using an extended version of Phast dispersion model UDM), as well as more simple methods based on rainout correlations without droplet modelling. Recommendations are made for the most accurate droplet size and rainout modelling. A modified CCPS UDM droplet size correlation has been shown to agree best against experimental rainout data.     

Optimal fire histories for biodiversity conservation

Fire is used as a management tool for biodiversity conservation worldwide. A common objective is to avoid population extinctions due to inappropriate fire regimes. However, in many ecosystems, it is unclear what mix of fire histories will achieve this goal. We determined the optimal fire history of a given area for biological conservation with a method that links tools from 3 fields of research: species distribution modeling, composite indices of biodiversity, and decision science. We based our case study on extensive field surveys of birds, reptiles, and mammals in fire‐prone semi‐arid Australia. First, we developed statistical models of species’ responses to fire history. Second, we determined the optimal allocation of successional states in a given area, based on the geometric mean of species relative abundance. Finally, we showed how conservation targets based on this index can be incorporated into a decision‐making framework for fire management. Pyrodiversity per se did not necessarily promote vertebrate biodiversity. Maximizing pyrodiversity by having an even allocation of successional states did not maximize the geometric mean abundance of bird species. Older vegetation was disproportionately important for the conservation of birds, reptiles, and small mammals. Because our method defines fire management objectives based on the habitat requirements of multiple species in the community, it could be used widely to maximize biodiversity in fire‐prone ecosystems. Historiales de Incendios Óptimos para la Conservación de la Biodiversidad     

Analysis of spatio-temporal land cover changes for hydrological impact assessment within the Nyando River Basin of Kenya

The spatio-temporal changes in the land cover states of the Nyando Basin were investigated for auxiliary hydrological impact assessment. The predominant land cover types whose conversions could influence the hydrological response of the region were selected. Six Landsat images for 1973, 1986, and 2000 were processed to discern the changes based on a methodology that employs a hybrid of supervised and unsupervised classification schemes. The accuracy of the classifications were assessed using reference datasets processed in a GIS with the help of ground-based information obtained through participatory mapping techniques. To assess the possible hydrological effect of the detected changes during storm events, a physically based lumped approach for infiltration loss estimation was employed within five selected sub-basins. The results obtained indicated that forests in the basin declined by 20% while agricultural fields expanded by 16% during the entire period of study. Apparent from the land cover conversion matrices was that the majority of the forest decline was a consequence of agricultural expansion. The model results revealed decreased infiltration amounts by between 6% and 15%. The headwater regions with the vast deforestation were noted to be more vulnerable to the land cover change effects. Despite the haphazard land use patterns and uncertainties related to poor data quality for environmental monitoring and assessment, the study exposed the vast degradation and hence the need for sustainable land use planning for enhanced catchment management purposes.     

Disruptive counterillumination and its anti-predatory value in the plainfish midshipman Porichthys notatus

The plainfin midshipman Porichthys notatus Girard occurs in nearshore waters off the western coast of North America. We found that the ventrally directed photophores of juvenile laboratory-grown P. notatus function in counterillumination. Their bioluminescence matched downwelling light to obscure the silhouette as viewed from below. P. notatus did not obligatorily counterilluminate at all times in appropriate light. A hydrodynamic stimulus, in addition to appropriate downwelling light, was required to induce counterillumination. This is perhaps an adaptation to conserve its Vargula-type luciferin, which is obtained from its diet. The angular distribution of light produced by P. notatus approximated that typical of downwelling light in the ocean. There was a direct relationship between downwelling irradiance and the maximum intensity of P. notatus luminescence. Insufficient light was produced to replace the light blocked by the fish under lighting conditions typical of the natural environment. The luminescence was, however, effective in eliminating the silhouette of P. notatus as observed with an image-intensifying camera and by dark-adapted human observers. Consequently, the effectiveness of counterillumination probably originates in part from the disruptive pattern of the luminous photophores. P. notatus from the Puget Sound population, which lacks a luciferin source and is non-luminous, displayed counterillumination behavior when its luminescent system was activated by force-feeding the fish with dried Vargula hilgendorfi. Experiments using adult P. notatus as predators on a mixed population of non-luminous (Puget Sound) and luminous (Santa Barbara Channel) juvenile P. notatus revealed that under conditions of dim overhead illumination non-luminous P. notatus were preyed upon at twice the rate of luminous individuals. This is the first experimental evidence suggesting that counterillumination is effective as an anti-predatory strategy. Received: 25 August 1998 / Accepted: 25 March 1999     

Leaching of hydrophobic Cu and Zn from discarded marine antifouling paint residues: Evidence for transchelation of metal pyrithiones

Leaching of Cu and Zn from a composite of discarded antifouling paint residues ([Cu] = 288 mg g⁻¹; [Zn] = 96 mg g⁻¹) into natural sea water has been studied over a period of 75 h. Total Cu and Zn were released according to a pseudo first-order reaction, with rate constants on the order of 0.3 and 2.5 (mg L⁻¹)⁻¹ h⁻¹, respectively, and final concentrations equivalent to the dissolution of about 8 and 2% of respective concentrations in the composite. Time-distributions of hydrophobic metals, determined by solid phase extraction-methanol elution, were more complex. Net release of hydrophobic Cu was greater in the absence of light than under a sequence of light-dark cycles; however, hydrophobic Zn release was not detected under the former conditions but contributed up to 50% of total aqueous Zn when light was present. These observations are interpreted in terms of the relative thermodynamic and photolytic stabilities of biocidal pyrithione complexes.     

Characterizing the trophy hunting debate on Twitter

Social media is an arena of debate for contentious political and social topics. One conservation topic debated online is the acceptability of trophy hunting, a debate that has implications for national and international policy. We used a mixed-methods approach (grounded theory and quantitative clustering) to identify themes in the trophy hunting debate on Twitter. We examined commonly co-occurring categories that describe people's stances on trophy hunting. We identified 12 categories and 4 preliminary archetypes opposing trophy hunting—activism, scientific, condemning, and objecting—whose opposition derived from different moral reasoning. Few tweets (22) in our sample of 500 supported trophy hunting, whereas 350 opposed it. The debate was hostile; 7% of tweets in our sample were categorized as abusive. Online debates can be unproductive, and our findings may be important for stakeholders wishing to effectively engage in the trophy hunting debate on Twitter. More generally, we contend that because social media is increasingly influential, it is important to formally contextualize public responses to contentious conservation topics in order to aid communication of conservation evidence and to integrate diverse public perspectives in conservation practice.     

A comparison of X-ray fluorescence and wet chemical analysis for lead on air filters from different personal samplers used in a bronze foundry

Portable X-ray fluorescence (XRF) technology may provide faster turn-around without compromising accuracy when assessing personal exposures to metals such as lead, but it has only been tested in limited field environments. This study is part of a series, where different sampler types are used to collect airborne lead in different environments for presentation to a portable XRF analyzer. In this case personal samples were taken at a bronze foundry where lead is added to an alloy of copper, zinc and iron to improve casting, using the closed-face 37 mm cassette, the 37 mm GSP or "cone" sampler, the 25 mm Institute of Occupational Medicine (IOM) inhalable sampler, the 25 mm Button sampler, and the open-face 25 mm cassette. Mixed cellulose-ester filters were used in all samplers. Following XRF analysis the samples were extracted with acid and analyzed by inductively coupled plasma optical emission spectroscopy (ICP). For lead, all five samplers gave correlations (r(2)) greater than 0.9 between the two analytical methods over the entire range of found lead mass, which encompassed both the action level and the permissible exposure limit enforced in the USA by the Occupational Safety and Health Administration (OSHA). However, a correction was required to adjust linear regression trendlines to give a 1 : 1 correlation for the average of three readings across the GSP sampler, and a similar correction was required for the single readings from the IOM sampler and the 25 mm filter cassette. The bias possibly is due to interference from other metals, possibly copper which can absorb the fluorescent radiation of lead. In the case of the Button sampler, the bias is larger, indicating a further source of error, perhaps due to the thickness of the deposit. However, in all cases, correction of the lead results did not greatly affect the overall percentage of samples where the XRF result was within 25% of the ICP result, although it did improve the overall accuracy of the results. The GSP, IOM and Button samplers are suitable candidates for further evaluation as compatible with on-site XRF analysis for lead and other metals. It is important to check carefully factory pre-set instrument calibrations, as a bias in the calibration for copper was observed.